Alkaloids: Chemical and Biological Perspectives

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Alkaloids: Chemical and Biological Perspectives

Related Titles of Interest Books CLARIDGE: High-Resolution NMR Techniques in Organic Chemistry GAWLEY & AUBE: Principles of Asymmetric Synthesis GRIBBLE & GILCHRIST: Progress in Heterocyclic Chemistry LEVY & TANG: The Chemistry of C-Glycosides PALYI: Advances in Biochirality RAHMAN: Studies in Natural Products Chemistry RAHMAN: Handbook of Natural Product Data ROMEO: Recent Advances in Phytochemistry SESSLER & WEGHORN: Expanded, Contracted and Isomeric Porphyrins WONG & WHITESIDES: Enzymes in Synthetic Organic Chemistry Major Reference Works BARTON, NAKANISHI, METH-COHN: Comprehensive Natural Products Chemisti BARTON & OLLIS: Comprehensive Organic Chemistry KATRITZKY & REES: Comprehensive Heterocyclic Chemistry I CD-Rom KATRITZKY. REES & SCRIVEN: Comprehensive Heterocyclic Chemistry II KATRITZKY, METH-COHN & REES: Comprehensive Organic Functional Group Transformations LEHN, ATWOOD, DAVIES. MACNICOL, VOGTLE: Comprehensive Supramolecular Chemistry SAINSBURY: Rodd's Chemistry of Carbon Compounds TROST & FLEMING: Comprehensive Organic Synthesis Journals BIOORGANIC & MEDICINAL CHEMISTRY BIOORGANIC & MEDICINAL CHEMISTRY LETTERS CARBOHYDRATE RESEARCH HETEROCYCLES (distributed by Elsevier) JOURNAL OF SUPRAMOLECULAR CHEMISTRY PHYTOCHEMISTRY TETRAHEDRON TETRAHEDRON: ASYMMETRY TETRAHEDRON LETTERS Full details of all Elsevier Science publications, and a free specimen copy of any Elsevier Science journal, are available on request from your nearest Elsevier Science office.

Alkaloids: Chemical and Biological Perspectives Volume Fifteen

Edited by

S. William Pelletier Institute for Natural Products Research and Department of Chemistry The University of Georgia, Athens

2001

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First edition 2001 Library of Congress Cataloging in Publication Data A catalog record from the Library of Congress has been applied for. British Library Cataloguing in Publication Data A catalogue record from the British Lilvary has been applied for.

ISBN:

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Transferred to digital printing 2005

Dedicated to Tuticorin Raghavachari Govindachari (1915.) T. R. Govindachari's contributions have been largely in the field of alkaloid chemistry. He was bom on July 30, 1915 in Madras (Chennai) India and obtained his B.Sc. (1934), M.Sc. (1936) and Ph.D. (1946) degreesfix)mthe University of Madras. He carried out post-doctoral work (1949) at the University of Illinois. He was mainly responsible for the structure elucidation of tylophorine and its congeners, tiliacorine, ancistrocladine, atalaphilline, and many other alkaloids. He isolated venenatine, isovenenatine and the papaya alkaloids carpaine, pseudocarpaine and assigned their structures. Diuing his stay at Illinois, he was associated with Professor Roger Adams and contributed to the structures of many pyrrolizidine alkaloids such as riddelliine, seneciophylline, arid senecionine from Senecia species. He was Professor of chemistry and Principal at Presidency College, Madras (1952-1962) and was director of the CIBA research Centre, Bombay (1963-1975). After retirement he directed work at the Amrutanjan Research Institute and the SPIC Science Foundation. Dr. Govindachari has an indefatigable interest in the study of Natural Products and has elucidated the structures of many novel oxygen heterocyclics and terpenoids like polyalthic acid and azadirachtins from the neem kernel extracts.

B. S. Joshi

This Page Intentionally Left Blank

vii

Preface Volume 15 of this series features four important reviews of research on alkaloids. Chapter I by B. S. Joshi, S. W. Pelletier and S. K. Srivastava is the first comprehensive review of the catbon-13 and proton NMR shift assignments and physical constants of diterpene alkaloids and their derivatives. In addition to the catalogue of spectral and physical data, the chapter includes a table of the occurrences of these alkaloids in various plant species, tables containing molecular formulas versus calculated high-resolution mass values, and calculated high-resolution mass values versus the molecular formulas of diterpenoid alkaloids, as well as seven tables summarizing the carbon-13 chemical shifts of various functional groups in diterpenoid alkaloids. Chapter 2 by J. Kim, Y.H. Choi and K.-P. Yoo is a fascinating review of the supercritical fluid extraction of alkaloids. This technique using basic modifiers, provides an alternative method for the extraction of alkaloids. Chapter 3 by S. Prabhakar and M.R. Tavares summarizes recent advances in the synthesis of Amaryllidaceae alkaloids, an important class of naturally-occurring bases and neutral compounds. The increased activity in the synthesis of these alkaloids over the last decade is undoubtedly due to the fact that certain members of this family possess interesting and useful biological properties. Many elegant syntheses, chiral and otherwise, of structures incorporating many asymmetric centres are reviewed. Chapter 4 by J.J. Li reviews radical cyclization reactions in the total synthesis of indole alkaloids. The use of free radical chemistry in the synthesis of alkaloids has grown markedly because of the mild reaction conditions, tolerance of a wide variety of functional groups, and the good stereoselectivities. Each chapter in this volume has been reviewed by at least one specialist in the field. The editor thanks these reviewers for their important contributions to this volume. Indexes for both subjects and organisms are provided. S. William Pelletier Athens, Georgia May 28,2001


ix

Contents ofPrevious Volumes Volume 1 1. The Nature and Definition of an Alkaloid S. William Pelletier 2. Arthropod Alkaloids: Distribution, Functions, and Chemistry Tappey H. Jones and Murray S. Blum

33

3. Biosynthesis and Metabolism of the Tobacco Alkaloids Edward Leete

85

4. The Toxicology and Pharmacology of Diterpenoid Alkaloids M H. Benn and John M. Jacyno 5. A Chemotaxonomic Investigation of the Plant Families of Apocynaceae, Loganiaceae, and Rubiaceae by Their Indole Alkaloid Content M Volkan Kisabiirek, Anthony J.M, Leeuwenberg, and Manfred Hesse

153

211

Volume 2 1. Some Uses of X-ray Diffraction in Alkaloid Chemistry Janet Finer-Moore, Edward Arnold, and Jon Clardy 2. The Imidazole Alkaloids RicharkK,Hill 3. Quinolizidine Alkaloids of the Leguminosae: Structural Types, Analyses, Chemotaxonomy, and Biological Properties A. Douglas Kinghom and Manuel F, Balandrin 4. Chemistry and Pharmacology of Maytansinoid Alkaloids Cecil R, Smith, Jr. and Richard G, Powell

49

105

149

X

Contents of Previous Volumes

5. ^^C and Proton NMR Shift Assignments and Physical Constants of Ci9-Diterpenoid Alkaloids S. William Pelletier, Naresh V. Mody, Balawant S. Joshi, and Lee C. Schramm

205

Volume 3 1. The Pyridine and Piperidine Alkaloids: Chemistry and Pharmacology Gahor B. Fodor and Brenda Colasanti 2. The Indolosesquiterpene Alkaloids of the Annonaceae Peter G. Waterman

I

91

3. Cyclopeptide Alkaloids Madeleine M, Joullie and Ruth F. Nutt

113

4. Cannabis Alkaloids Mahmoud A. ElSohly

169

5. Synthesis of Lycopodium Alkaloids Todd A. Blumenkopf and Clayton H. Heathcock

185

6. The Synthesis of Indolizidine and Quinolizidine Alkaloids of Tylophora, Cryptocarya, Ipomoea, Elaeocarptis, and Related Species R. B. Herbert 7. Recent Advances in the Total Synthesis of Pentacyclic Aspidosperma Alkaloids Larry E, Overman and Michael Sworin

Volume 4 1. Amphibian Alkaloids: Chemistry, Pharmacology and Biology John W. Daly and Thomas F. Spande

241

275

Contents of Previous Volumes 2. Marine Alkaloids and Related Compounds William Fenical 3. The Dimeric Alkaloids of the Rutaceae Derived by Diels-Alder Addition Peter G. Watermann 4. Teratology of Steroidal Alkaloids Richard F. Keeler

x\ 275

331

389

Volume 5 1. The Chemistry and Biochemistry of Simple Indolizidine and Related Polyhydroxy Alkaloids Alan D. Elhein andRussellJ. Molyneux 2. Structure and Synthesis of Phenanthroindiolizidine Alkaloids and Some Related Compounds Emery Gellert

55

3. The Aporphinoid Alkaloids of the Annonaceae Andre Cave, Michel Lehoeuf, Peter G. Waterman

133

4. The Thalictrum Alkaloids: Chemistry and Pharmacology Paul L Schiff. Jr.

271

5. Synthesis of Chephalotaxine Alkaloids Tomas Hudlicky, Lawrence D. Kwart, and Josephine W. Reed

639

Volume 6 1. Chemistry, Biology and Therapeutics of the Mitomycins William A. Remers and Robert T. Dorr 2. Alkaloids of Tabernaemontana Species Teris A. van Seek and Marian A.J. T. van Gessel

75

xii


3. Advances in Alkaloid Total Synthesis via Iminium Ions, a-Aminocarbanions and a-Aminoradicals David J. Hart

4. The Biosynthesis of Protoberberine Alkaloids Christopher W, W. Beecher and William J. Kelleher

5. Quinoline, Acridone and Quinazoline Alkaloids: Chemistry, Biosynthesis and Biological Properties Michael F. Grundon

227

297

339

Volume 7 1. Homoerythrina and Related Alkaloids /. Ralph C. Bick and Sirichai Panichanum 2. Carbon-13 NMR Spectroscopy of Steroidal Alkaloids Pawan K, Agrawal Santosh K. Srivastava, and William Gqffield 3. Carbon-13 and Proton NMR Shift Assignments and Physical Constants of Norditerpenoid Alkaloids S. William Pelletier and Balawant S. Joshi

43

297

Volume 8 1. Curare Norman G. Bisset

2. Alkaloid Chemistry and Feeding Specificity of Insect Herbivores James A. Saunders, Nichole R. O'Neill, and John T. Romeo

151

3. Recent Advances in the Synthesis of Yohimbine Alkaloids Ellen W. Baxter and Patrick S. Mariano

197

4. The Loline Group of Pyrrolizidine Alkaloids Richard G, Powell and Richard J, Petroski

320


xiii

Volume 9 1. Taxol M £ . Wall and M. a Want 2. The Synthesis ofMacroline Related Sarpagine Alkaloids Linda K. Hamaker and James M, Cook

23

3. Erythrina Alkaloids Amrik Singh Chawla and Vijay K. Kapoor

85

4. Chemistry, Biology and Chemoecology of the Pyrrolizidine Alkaloids Thomas Hartmann andLudger Witte

155

5. AlkaloidsfromCell Cultures of Aspidosperma Quebracho-Bianco P. Obitz, J. Stdckigt, L A. Mendonza, N, Aimi andS.-i. Sakai

235

6. Fumonisins Richard G. Powell and Ronald D. Planner

247

Volume 10 1. AlkaloidsfromAustralian Flora /. R. C. Bick 2. Pyridine and Piperidine Alkaloids: An Update Marilyn J, Schneider

155

3. 3-Alkylpiperidine Alkaloids IsolatedfromMarine Sponges in the Order Haplosclerida Raymond J. Andersen, Rob W. M Van Soest and Fangming Kong

301

4. P-Carboline and Isoquinoline AlkaloidsfromMarine Organisms Billl Baker

357

Contents of Previous Volumes Volume 11 1.

The Tlialictnm Alkaloids: Chemistry and Pharmacology (1985 - 1995) Paul L Schiff. Jr.

1

2.

Taxine Gioxwtni Appendino

237

3.

The Alkaloids of South American Menispermaceae Maiy D. Menachen^

269

4.

The Chemistry and Biological Activity of Calystegines and Related A'brtropane Alkaloids Russell J. MolyneiLX, Robert J. Nash, and Naoki Asano

303

5.

Polyhydroxylated Alkaloids that Inhibit Glycosidases Robert J. Nash, Naoki Asano, and Alison A. Watson

345

Volume 12 1.

Acronycine-type Alkaloids: Chemistry and Biology Frangois Tillequin, Sylvie Michel, and Alexios-Leandros Skaltsounis

1

2.

Solanum Steroid Alkaloids — an Update Helmut Ripperger

103

3.

Synthesis and Structure-Activity Studies of Lissoclinum Peptide Alkaloids Peter Wipf

187

4.

Pyroglutamate as a Chiral Template for the Synthesis of Alkaloids Michael B. Smith

229

5.

Analysis of Alkaloids by Capillary Electrophoresis and Capillary Electrophoresis — Electrospray Mass Spectrometry Joachim Stockigt, Matthias linger, Detlef Stockigt, and Detlev Belder

289

Contents of Previous Volumes 6.

Oxidation of Anthelmentic Marcofortine A, an Indole Alkaloid Byung H. Lee, Michael F. Clothier, and Gate I. Kornis

xv 343

Volume 13 1.

Alkaloids from Amphibian Skins John W. Daly, H. Martin Garraffo and Thomas F. Spande

1

2.

Naturally Occurring Cyclotryptophans and Cyclotryptamines Uffe Anthoni, Carsten Christophersen and Per Halfdan Nielson

163

3.

Recent Research on Pyrrole Alkaloids Philip W, LeQiiesne, Ying Dong and Todd A. Blythe

237

4.

Recent Developments in the Chemistry of Norditeipenoid and Diterpenoid Alkaloids Balawant S. Joshi and S. William Pelletier

289

5.

New Approaches to the Syntheses of Piperidine, Izidine, and Quinazoline Alkaloids by Means of Transition Metal Catalyzed Carbonylations Iwao Ojima and Donna M. Ma

371

Volume 14 1.

The Bisbenzylisoquinoline Alkaloids - A Tabular Review Paul L Schiff, Jn

2.

Alkaloids from Malaysian Flora

285

3.

Applications of Palladium Chemistry to the Total Synthesis of Naturally Occurring Indole Alkaloids Jie Jack Li

437

TohSeokKam

1


xvii

Contributors Young Hae Choi, College of Phannacy, Seoul National University, Seoul 151-742, KOREA. Balawant S. Joshi, Institute for Natural Products Research, University of Georgia, Athens, GA 30602, U.S.A. Jinwoong Kim, College of Pharmacy, Seoul National University, Seoul 151-742, KOREA. Jie Jack Lie, Parke-Davis Pharmaceutical Research Division, Warner-Lambert Company, 2800 Plymouth Road, Ann Arbor, MI 48105, U.S.A. S. William Pelletier, Institute for Natural Products Research and The Department of Chemistry, University of Georgia, Athens, GA 30602, U.S.A. Sundaresan Prabhakar, Department of Chemistry, Faculty of Science and Technology, New University of Lisbon, 2825-114 Monte de Caparica, PORTUGAL. Santosh K. Srivastava, Central Institute of Medicinal and Aromatic Plants, Council of Scientific & Industrial Research, PO CIMAP, Lucknow-226015, INDIA. M. Regina Tavares, Department of Technology of Chemical Industries, INETI, 1649-038 Lisbon, PORTUGAL. Ki-Pung Yoo, Department of Chemical Engineering, Sogang University, Seoul 121-742, KOREA.


xix

Contents 1.

2. 3.

4.

Carbon-13 and Proton NMR Shift Assignments and Physical Constants of Diterpenoid Alkaloids Balawant S. Joshi, S. William Pelletier, and Santosh K, Srivastava

1

Supercritical Fluid Extraction of Alkaloids Jinwoong Kim, Young Hae Choi, and Ki-Pung Yoo

415

Recent Advances in the Total Synthesis of Amaryllidaceae Alkaloids Sundaresan Prabhakar and M. Regina Tavares

433

Applications of Radical Cyclization Reactions in Total Syntheses of Naturally Occurring Indole Alkaloids Jie Jack Li

573

Subject Index

623

Organism Index

633


Chapter One

Carbon-13 and Proton NMR Shift Assignments and Pliysical Constants of Diterpenoid Alkaloids Balawant S. Joshi and S. Wtlliam Pelletier Institute for Natural Products Research and the Department of Chemistry The University of Georgia Athens, Georgia 30602-2556 U.S.A. Santosh K. Srivastava Central Institute ofMedicinal and Aromatic Plants Council ofScientific & Industrial Research PO'CIMAP, Lucknow'226015 India

CONTENTS 1. 2. 3. 4.

Introduction '^C-Chemical Shifts of Various Functional Groups of C2o-Diterpenoid Alkaloids Index of Naturally Occurring Diterpenoid Alkaloids and their Derivatives Calculated High Resolution Mass Values and Molecular Formulas of Diterpenoid Alkaloids 5. Occurrence ofDiterpenoid Alkaloids in Plant Species 6. Catalogue of Spectral Data and Physical Constants of Naturally Occurring Diterpenoid Alkaloids and their Derivatives

2 5 13 22 37 48

2

1.

B.S. Joshi, S.W. Pelletier and S.K. Srivastava

Introduction

Diterpenoid alkaloids have been isolated from the genera of the families Ranunculaceae (Aconitum, Comolida, Delphinium^ Thalictrum), Garryaceae (Garraya), Rosaceae (Spiraea), and Compositae (Inula). These alkaloids can be divided into two broad categories: norditerpenoid alkaloids (based on a Ci9-skeleton) and the diterpenoid alkaloids (based on a C2o-skeleton)J The chemistry of the diterpenoid alkaloids has been reviewed in earlier literature. ^*^*^*^ Structural elucidation of norditerpenoid alkaloids is mostly straightforward since almost all the alkaloids fall in one major skeleton-type and have well defmed substitution and configurational pattern. In addition ^^C NMR data for norditerpenoid alkaloids is readily available to compare chemical shift data of alkaloids having closely related structures.^'^ Structure determination of the diterpenoid alkaloids (C20) has been a challenging task because of the diverse skeleta of these alkaloids. During the period (-1962-1972), many of the structures were determined by X-ray crystal structure determination. The development of high resolution NMR and Mass spectral instruments has facilitated the structure elucidation and determination of the stereochemistry of the diterpenoid alkaloids. The structures of more than 240 naturally occurring diterpenoid alkaloids have been determined in the past twenty five years making use of '^C NMR studies. The diterpenoid alkaloids are derived from tetra- or pentacyclic diterpenes in which C(19) and C(20) are linked with the nitrogen of |3-aminoethanol, methyl or ethylamine to form a heterocyclic ring. These alkaloids can be divided in two broad types namely, atisanes and the kauranes. The atisane skeleton contains the [2,2,2]-bicyclic ring system with the C(15)-C(16) bridge attached at C(12). This ring system incorporates an ent-aiisane skeleton, but does not obey the isoprene rule. The atisane group has been subdivided into four subtypes Al, A2, A3, and A4 as shown in Figure 1. The kaurane skeleton possesses a [3,2,l]-bicyclic ring system with C(15)- C(16) bridge connected to C(13), forming thefive-memberring D. These alkaloids are modeled on an e/7/-kaurane nucleus and obey the isoprene rule. The kaurane-type alkaloids have been divided into three subtypes Bl, B2, and B3. In contrast to the norditerpenoid alkaloids, the diterpenoid alkaloids are less oxygenated compounds. The diterpenoid alkaloids are found to be oxygenated at the C(l), C(2), C(3), C(6), C(7), C(9), C(ll), C(13), C(14), C(15), C(17), or C(19) positions. A large majority of alkaloids are oxygenated on three or four of the carbon atoms. Some unusual diterpenoid alkaloids. Acofine is the only example of the B3type having a chlorine atom at C(l) and cardionine is the sole alkaloid with a hydroxy 1 group attached at C(12). Methoxyl groups are commonly substituted on many of the carbon atoms in norditerpenoid alkaloids. Among the diterpenoid alkaloids, only two alkaloids of the B3-type, lingshanine and lingshanone, have a methoxyl group at C(l). Septatisine and septedine are the only examples of atisane-type (Al) diterpenoid alkaloids in which C(20) of the oxazolidine ring is bridged with C(14). In barbeline, barbisine, delgrandine, vakognavine and 15- deacetylvakognavine, all belonging to the A2type, the N-C(19) bond is broken and carbon-19 bears an aldehydic group.

Carbon-13 and Proton NMR Shift Assignments 13

i>3 i^'u

21--

A1

13

M

1 2 ( ^ 21-

-f-N 3U / ^

19

v

20

|10H

Is

.H

17

17 11

lie

]16

1

Jl5

|8

21-

^ 7

(J

a ^

it >

19

Me

J15

Is ^yi

^H

6

Me

18

18

A4

A3

Figure 1 The naturally occurring diterpenoid alkaloid miyaconitinone (Al-type) contains a diketone at the C(6), C(7) positions and caidionidine (Al-type) possesses an anhydride group in the B-ring between C(6), C(7). In albovionitme (Al-type), the C(18) methyl

4

BS. JoshU S.W. Pelletier and S.K. Srivastava

group is oxidized to a hydoxymethyl and the N-C(20) bond is cleaved, with the formation of a ketone at C(20). In delnudine, (A2-type) the C(12)-C(16) bond is broken and a new bond is established between C(l 1) and C(16). Eight dimeric diteipenoid alkaloids, all constituting an Al-type dimerized to an A3-type have been isolated from the mother liquors of Delphinium staphisagria L. All of these alkaloids are dimerized at C(17), C(17') and form a pyran ring at the C(16), (C15') position. These alkaloids are staphidine, staphigine, staphimine, staphinine, staphirine, staphisagnine, staphisagrine and staphisine. Coryphidine and coryphine are alkaloids of the A3 and Al-type, in which the C(17) carbon is attached to hexahydro-7Vmethylindoline. In tangirine, an Al-type diterpenoid alkaloid, C(17) carbon is attached at the C(8) position to the naturally occurring norditerpenoid alkaloid 6-benzoyl heteratisine. Zeraconine and zeraconine-iV-oxide are A2 type alkaloids in which the C (17) carbon is linked to the phenolic oxygen of/7-(Ar,Af-dimethylaminoethyl) phenol to form an ether. In pukeensine, the C(17) carbon atom of one of the A4 -type diterpenoid alkaloid forms an ether linkage with the ethanolamino group of a second diterpenoid alkaloid of the A4-type. The present catalogue provides proton and/or carbon-13 NMR chemical shift assignments and physical constants for many of the naturally occurring diterpenoid alkaloids and their derivatives. The literature search is not intended to be exhaustive. It is hoped that the '^C NMR data bank will serve as a useful guide for determining the structures of newly isolated alkaloids.

References: 1. TK Devon and AI Scott, "Handbook of Naturally Occurring Compounds" Vol. 2, pp. 188,241-248, Academic Press, N.Y. 1972. 2. SW Pelletier and LH Kieth, in "The Alkaloids" (RHF Manske ed.), vol. 12, Chapter 2, pp. 136-202, Academic Press, N. Y. 1970. 3. SW Pelletier and NV Mody, in "The Alkaloids" (RGH Rodrigo, ed.). Vol. 18, Chapter, 2, pp. 99-211, Academic Press, N. Y. 1981. 4. MS Yunusov, Diterpenoid Alkaloids in '*Natural Product Reports", Vol. 3, p. 451 1986; Vol. 8, p. 499,1992, The British Chemical Society, London. 5. BS Joshi and SW Pelletier, Recent Developments in the Chemistry of Norditerpenoid and Diterpenoid Alkaloids in "Alkaloids: Chemical and Biological Perspectives", (SW Pelletier, ed.). Vol 13, Chapter 4, pp. 292-2362, Pcrgamon Press, Amsterdam, 1999. 6. SW Pelletier, NV Mody, BS Joshi and LC Schramm, in "Alkaloids: Chemical and Biological Perspectives", (SW Pelletier, ed.),.Vol. 2, Chapter 5, pp. 205-462, John Wiley and Sons, N.Y. 1984. 7. SW Pelletier and BS Joshi, in "Alkaloids: Chemical and Biological Perspectives", (SW Pelletier, ed.),.vol. 7, Chapter 3, pp. 297-564, Springer Verlag, N. Y. 1991.

Carbon-13 and Proton NMR Shift Assignments

5

2. '^C-Chemical Shifts of Varioiis Functional Groups of Cio-Diterpenoid Allcaloids Table 1 TypeAl Vi2

17.

zr 21---I"

19

Functional Group C(l)-H2 C(l)-H2 If

ft

C(2)-H2 C (2)-0R C(3)-H2 tf

C (3)-OR C(4) rt

C(5)-H C (6)-ketone C(7)-H2 tf

C(8) C (9)-H C(9)-OH C(10) ft

C(ll)-H2 If

C(12)-H ft

C (13)-H2 ft

C(13)-ketone C (14).H ft

C(15)-H2 ft ft

C(16)

M«

Chemical Shift Range ppm 30-32 34-36 37-40 41-48 18-21 67-69 30-33 44-45 76-78 35-37 37-42 55-62 200-212 50-52 48-52 42-44 48-51 78-80 43-45 47-49 22-24 36-38 53-54 38-40 28-29 35-36 210-212 43-45 58-59 28-29 34-35 41-43 141-143

Remarks General range C(2)-OR,C(3)-OR C(2)-OH/C(3)-OH A^.CH2-CH2-0-C(19) General range C{3)-0R General range C(2)-0R General range General range C(3)-0R C (6)-ketone No subst. on C (7), C (9) C (6)-ketone; no subst. on C(9) C (6)-ketone; C (9)-0H C (6)-ketone Nosubst.onC(ll),C(15) General range Nosubst.onC(l),C(9), C(ll) C{9)-0H C(13)-ketone C(9)-OH;noC(13)-ketone C(13)-ketone No C (13)-ketone C(16)-0H General range General range NoC(13)-ketone C(13)-ketone C {9)-0H General range C (9)-0H, C (16)-0H C(13)-ketone

B.S. Joshi, S.W. Pelletier and S.K. Srivastava Functional QrQup tf

C(17)-H2 II

C(18)-H3 C(19)-H2 II

C (20)-H

Chgmiwl ghjft l^ngg ppm

Remarks

151-152 102-103 110-112 24-29 53-60 93-98 71-72

NoC(13)-ketone NoC(13)-ketone C(13)-ketone General range General range C (19)-0-CH2CHr General range

Table 2 TypeA2 13

^^ Û

Functional Group

Chemical Shift Range ppm

Rem^rkg

C(l)-H2 C(l)-H2

33-35 30-36 44-46 68-79 19-21 26-28 68-71 75-76 210-211 33-35 37-41 50-51 71-72 36-38 42-44 60-62 50-55 63-65 98-100 32-37 27-30 43-45 44-46 49-50 53-55 65-66

General range C (2)-OH, -OCOR C (2)-ketone General range General range C(1)-0H General range C (3)-0H General range General range C (2)-a-0H, -OCOR C (2)-ketone General range General range C (2)-ketone General range C(9).p-0H General range General range General range C(9)-P-0H,C(15)-P-0H General range C(15)-0H Nosubst.onC(ll),C(15) C(11)-0H C(ll)-ketone

It

C(1)-P-0R C(2)-H2 C(2)-H2 C (2)-a-0R II

C (2)-ketone C(3)-H2 C (3)-0H C(4) II

C (5)-H II

C (6)-H C (6)-0H C(7)-H2 II

C(8) C (9)-H

Carbon-13 and Proton NMR Shift Assignments Functional Group


Remark?

C (9)-P-0H C (lO)-H C(ll)-H2

79-81 50-55 22-23 37-40 210-212 72-76 33-36 52-53 27-33 68-72 75-80 67-68 211-213 42-45 51-52 61-62 78-80 27-30 72-76 142-147 154-156 107-110 28-30 25-27 60-64 58-60 90-92 68-75

General range General range General range C (9)-p.0H General range General range General range C(ll)orC(13)-OHorketone General range General range C(11)-0H C(13)-ketone General range General range C(13)-OH C(13)-ketone General range General range General range General range C(15)-p-OH General range General range C (3)-a-0H General range C (3)-a-0R General range General range

n

C(ll)-ketone C(11)-0H C (12)-H C(13)-H2 C(13)-0H C(13)-0H C(13)-0H C(13)-ketone C (14)-H C(14)-p-0H C(15>H2 C(15)-p-0H C(16) It

C(17)-H2 C(18)-H3 11

C(19)-H2 It

C(19)-OH C (20)-H Table 3 Type A3

rvi2 ^

/

»

^

JN^^ '^*-L F^

^.

'

/ ^

19

Functional Group

^ Chemical Shift Ranee ppm

Remarks

C(l)-H2 C(l)-H2 C(2)-H2 C(2)-H2 C(3)-H2 C(4) C (5)-H

40-43 35-37 22-24 19-20 39-41 33-34 48-52

General range N=C (20) General range N = C(20) General range General range General range


Fwgtipn»l Qrow

Chgmjggl Shif it Rangg ppm

Remarks

C(6)-H2

17-18 35-37 20-25 31-36 72-77 212-216 36-38 44-48 51-53 39-42 37-38 40-41 28-29 35-37 26-28 25-26 215-220 72-77 202-204 152-158 109-110 26-27 56-60 97-99 52-54 93-94 164-166

General range C (7)-ketone C(7)-0H General range General range General range C(14)orC(15)-P-OH C(15)-ketone C(7)-ketone,C(15)-p.OH General range General range C(20)-O.CH2CH2General range General range General range General range General range General range General range General range General range General range General range General range General range General range -N=CH(20)

H It

C(7)-H2 C (7)-a-0H C (7)-kctone C(8) If II

C (9)-H C{10) II

C(ll)-Hz C (12)-H C(13)-H2 C(14)-H2 C (14)-ketone C(15)-0H,0Ac C(15)-ketone C(16) C(17)-H2 C(18)-H3 C(19)-H2 C (19)-OCH2 C (20)-H2 C (20)-OCH2 C (20)-H2 Table 4 Type A4

1

Tio *% Te 1 ^1

/ ^ ^JH 6

ia

1^®

Functional Group


Rem^k?

C(l)-H2 C (l)-a-OH C(2)-H2

40-41 70-72 21-23 30-32 69-70 27-30 68-69

General range General range General range C (l)-OH present General range General range General range

II

C (2)-a-0H C(3)-H2 C(3)-a-0H

Carbon-13 and Proton NMR Shift Assignments Functional Group ft

C(4) C (5)-H H

C(6)-H2 II

C(7)-H C(7>O-C(20) C(8) C(9) II

C(10) II

C(ll)-H2 II

C (12)-H II

C (13)-H2 C (13)-0R C(14)-H2 C(15)-H2 C(15)-0R C(16) C(16)-0H C(17) C(17) C(17) C(18)-H3 C(19)-H2 C(19)-H2 C (19)-OR C (20)-H C(20)-H C (20)-H C (21)-H3 C (21)-CH2CH2-0

Chemical Shift Rangeppm

Rfemarks

36-38 34-36 50-52 41-45 23-26 70-72 41-44 72-76 41-44 43-46 50-54 34-35 48-51 23-25 72-73 42-46 30-36 22-25 70-72 22-28 20-22 77-86 150-156 79-81 109-112 68-72 45-46 25-27 57-59 52-54 93-95 67-69 86-88 68-70 42-45 52-58

C (20)-O-C (7) present General range C(l)-a-OH present General range General range C(7)-p-0R present General range General range General range General range C(1)-0H present General range C(1)-0H present General range C (7)-0H p present General range C (7)-0-C (20) present General range General range General range General range General range General range CH20HatC(17) General range CH20HatC(17) Epoxide on C(16)-C (17) General range General range C (20)-O-(7) present General range General range C (20)-O-C (7) present C(1)-0H present General range General range

Table 5 Type Bl 12

Sj3

1

>S. i^rC^ C

20

17

' KS:s»CH2

2 / S < X ^ ^^Pj^ IS

18

10


Functional Group


41-42 46-47 82-84 C(l)-OH C(2Hl2 22-23 71-72 C (2).a-0H M 76-77 36-37 C(3)-H2 " 42-43 36-37 C(4) M 40-41 45-46 C (5)-H 78-79 C (5)-P-0H 24-25 C(6)-H2 66-68 C (6)-a-0M 34-35 C(7).U2 It 39-40 52-53 C{S) 56-59 C (9)-H 51-52 C(10) C(ll)-a-OH,-OCOR 71-73 70-76 C(12)-a-0C0R 54-55 C(13)-H 52-54 C(14)-H 36-37 C(I5)-H2 148-150 C(16) 107-108 C(17).H2 23-25 C(18)-H3 61-62 C(19)-H2 168-169 C(19)=N63-65 C (20)-H

Remarks General range C(2)-a-0H General range General range General range C(l)-a-OH General range C (2)-a.0H C(5)-P-0H C(19) = NGcneral range General range General range C (5)-p-0H General range C(6)-a-0H General range C(11)--0H,0C0R General range General range C(ll)-a-OH,-a-COR General range General range General range General range General range General range General range General range General range

C(I)-H2 •1

Table 6 Type B2

12 1

20

^ S ^ .7

Acetylcardiopetamine 3-O-Acetylcardiopine 3-O-Acetylcardiopinine 13-0-Acetyl-15-dchydrocardiopetainine 15-0-Acetyl-13-dehydrocardiopetaminc 11 -0-Acetyl-1,19-dehydrodenudatine 3-O-Acelyl-2,20-dehydro-16,17-dihydro(14,20-5cco)hetidine 2-0-Acetyl-l 3-dehydro-11 -e/i/-hetisine 12-0-Acetyl-1,19-dehydrolucidusculine 12-e/;i-0-Acety 1-1,19-dehydronapelline 7-0-Acetyldelgrandine 13-0-Acetyl-9-deoxyglanduline 14-O-Acety 1-9-deoxyglanduline 1 l-0-Acetyl-2J 3-didehydrohetisine 13-O-Accty 1-2,11-didehydrohetisine 13-O-Acetylfissumine 13-0-Acetylglanduline 13-O-Acetylgoinandonine 2-0-Acetylhetisine 13-O-Acetylhetisine 13-0-Acetylhetisine-2-one 2-Acctyl-3-hexahydrobenzoyl-16,17dihydrohetidine 15-0-Acetyl-9-hydroxynominine 11-O-Acetylisohypognavine 11 -0-Acctyl!epenine 1 -O-Acetylluciculine 12-0-Acety llucidusculine 12-0-Acety Inapelline 12-O-Acetylnapelline-N-oxide 15-0-Acetylryosenamine

Structure Type

X-Ra)f

D D D D N N D D D N N D

B3 A3 A2 A2 A2 A2 A2 A2 A2 A2 B3 A3

__ -

D N N N N N D D D N N D N/D N/D D D N N N N N N D

'H

"c

~ ~ —

X X X X X X X X X X

_, X X X X X X X X X X X

A2 A4 B3 A2 A2 A2 A2 A2 A2 A2 A4 A2 A2 A2 Al

— — — — X .. ~

X X X X X X X X X X X X X X X

— X X X X X X X X X X X X X X

A2 A2 A4 83 83 83 83 A2

~ ~ ~ ~ -

X X X X X X X X

~ X X ~ — ~ ~

14 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76

B.S. Joshi, S.W. Pelletier and S.K. Srivastava 15-O-Acetylsczukinine 2-0-Acctylscplcnlriosine 15-O-Aceiylsongoraniine A^-Acelylspiradinc A 6-()-Acctylspiradine A Acofinc Acoridine Acorienlinc Acozcrinc Acsinatidine Acsinaline Ajaconinc Ajaconium chloride Albovionitinc Andersobine Andersobine-19-/7-Af,N-dimcthy laminobenzoate Anoptcrimine Anoplcriminc-//-oxidc Anoptcrinc (anopteryl-U,12-ditigtate) Anoplcry I-11 a-4'-hydroxybenzoalc-12atiglate Anoptcryl I2a-tiglate (I la-dcstigloyianopterine Apomiyaconine Atidine Atisine Atisinc-15-one Atisine-N,20-azomethine Atisinium chloride (Guan Fu Base G) Azitine Barbaline Barbisine 1 la-Benzoyl-7p-hydroxy-l la-destig loylanopterine(7p-Hydroxyanopteryil la-benzoate-l2a-tiglate) U-Benzoylkobusinc 15-Benzoylkobusine 6-Benzoylpseudokobusine 11 -Benzoylpseudokobusine 15-Bcnzoylpseudokobusine Brunonine Cardiodine Cardionidine Cardionine Cardiopetamine

D N D D D N N N N D N N D N N D

A2 A2 B3 Al A2 B3 A2 A2 Al A2 A2 A4 A3 Al A2 A2

-. -. X —

N N N N

— ~ — -. — — —

X X — X X X X X X — X X X X X

X X — ~ — X X X — X X X X X X

Bl Bl Bl Bl

~ ~ X —

X X X X

X X X ~

N

Bl

~

X

..

D N N D D N/D N N N N

Al A3 A3 A3 A3 A3 A3 A2 A2 Bl

X — — ~ X .X X

X X X X ~ ~ X X X X

X X X X X X X X X

D D D D N N N N N N

A2 A2 A2 A2 A2 A3 A2 Al A2 A2

« — X — X

X X X X X X X X X X

X X X X X

-

.

•

Carbon-13 and Proton NMR Shift Assignments 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114

Cardiopidine N Cardiopimine N Cardiopine N Cardiopinine N Chcllespontinc N Chiianfunine N Contorine (2-OAcctyl-3-anisoylhetidine) N Conlorsine (2-0-AcetyI-3-isobiUyr>'l N hetidinc) Contortinc (2-Acelyl-3(25)-mcthylbulyryl N hetidine) Coryphidine N Coryphine N Cossonidine N Cossoninc N Crassicaulinc B N Cuauchichicine N 16-c/;/-Cuauchichicine N Cuauchichicine-M20-azometliinc N 11,12,16-Cyclopropyl-16,17-dihydro D hetisane 2-Deacelylheterophynoidine N/D 15-DeacetylspiramineF D 15-Deacetylvakognavine N Ar-Deethyl-iV-acetyl-l,12,15-0-triacclyl D napelline N JV-Dcethyl-1,19-dchydrolucidusculine D 13 -Dehydrocardiopelamine D l5-Dehydrocardiopetaniine 2-Dehydrocardiopimine D 15-Dchydrocossonidine D D 3 -Dehydro-1 -desacetoxy-1,2-dehydro cardiopine D 3-Dehydro-1 -desacetoxy-1,2-dehydro cardiopinine D 2-Dehydro-l 1,13-O-diacetylhetisine D 13-Dehydro-2,11 -O-diacetylhetisine 2,20-Dehydro 16,17-dihydro-(14,20-5cco) D hetidine D 15,16-Dehydro-16,17-dihydrotatsirine ~ 11 -Dehydrohetisine N/D 1,19-Dchydrolucidusculine N 1 l-epi-1,19-dehydrolucidusculine N 12-C/7M ,19-dchydronapelline 1,19-Dehydronapelline (1,19-Dehydroluc N/D iculine)

15

A2 A2 A2 A2 Al B3 Al Al

.— .~ — — X X

X X X X X X X X

X X X X X X X X

Al

X

X

X

A3 Al A2 A2 A2 B2 B2 B2 A2

.. X ~ — «X .— X

X X X X X X X X X

X X X X — X X X ~

Al A4 A2 B3

_ ~ — -

X X X X

X X X X

B3 A2 A2 A2 A2 A2

.. — — — — -

X — X X X X

X X X ~ X X

A2

-

X

X

A2 A2 A3

.. — -

X X X

X X X

A2 A2 B3 B3 B3 B3

.. — —

X X X X X X

X X X — X X

~

~ ~

•

16 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158

B^. Joshi, S.W. Pelletier and S.K. Srivastava 13-Dehydropaniculatine 15-Dehydroryoscnamine Delatisine Dclbidine Delftssinol Delgrandine Delnudine Delnuttaline Delnuttidine Delnutline Dcnudatine 11'Desbenzoylcardiopetamine Ar-Desethylsongoraminc(norsongoraminc) 2-Desmethylbutyfylcardiopine N-Dcsmethyl'Nfi'SecO'S'hydroxycpiscop alidine-6-cathylate 1 la-Destigloylanopterinc (Anopteryl-l2a tiglate) 9,19-C7-Diacctylacsinatine 15-0,22-MDiaccty latidine 6,1 l-O-Diacetylcardionine (Basic) N,\ l-ehydroIucidusculine 1 l-epi' 1,19-Dehydrolucidusculine Spiradine F Spiramine A Spiraminc B Subdesculine

C24H33NO4

MW

401.2202 3-(9-Acetyl-2,2-dehydro-16,17-dihydro-(14,20 seco hetidine) Acoridine

C23H31NO5

MW

401.2566 11-0-AcetylIepenine 1 -OAcetylluciculinc 12-0-Acetylnapelline Lucidusculine (15-0-Acety Inapelline) 12-epi-Lucidusculine Spiramine F Spiramine I

C24H35NO4

MW

403.2359 13-0-Acety Igomandonine

C23H33NO5

MW

409.1889 7,1 l-O-Diacetylorientinine

C24H27NO5

MW

411.2046 13-0-Acetylfissumine 2-Dehydro-11.13-0-diacety Ihetisine 13-E>ehydro-1,11 -0-diacetylhetisine 1 l,13-(9-Diacetylhetisine-2-one 13,15-Di-O-acetyl venuluson

C24H29NO5


29

MW

411.2410 Anopterimine-iV-oxide

C25H33NO4

MW

411.2773 1,15-0-Diacetyl-16,17-dihydrosongorine

C26H37NO3

MW

413.1838 Miyaconitinone

C23H27NO6

MW

413.2202 2,11-0-Diacetylhetisine 11,13-(7-Diacetyhetisine 2,15-0-Diacetylryosenaminol

C24H3,N05

MW

413.2566 Spiramine L Spiramine M Yesodine

C25H35NO4

MW

415.1995 Miyaconitine

C23H29NO5

MW

415.2359 Cardionine Spiramine R

C24H33NO5

MW

417.2304 11-Benzoylkobusine 15-Benzoylkobusine

C27H31NO3

MW

417.2515 12-0-Acetylnapelline-Moxide Flavidine Guan Fu Base Z Thalicsiline

C24H35NO5

MW

427.2359 Geyerine

C25H33NO5

MW

427.2723 11,15-0-Diactyldenudatine

C26H37NO4

MW

429.2151 Guan Fu Base A

C24H3,N06

MW

429.2879 15-0,22-iV-Diacetyldihydroatisine 15,-0,22-A^Diacetyldihydix)veatchine

C26H39NO4

30


MW

431.2097 15-Dehydroryosenamine

C27H29NO4

MW

433.2253 6-BenzoyIpseudokobusine 11-Benzoylpseudokobusine 15~Benzoy Ipseudokobusine Crassicauline B Isohypognavine Ryosenamine

C27H3,N04

MW

433.2828 Isopropylidinechuanfunine

C25H39NO3

MW

435.2540 Acofme

C25H38CINO3

MW

439.1930 6-ImidazoylthiocarbonyIpseudokobusine

^24^29 3 3

MW

441.2151 15-0-Acetyl Sczukinine

C25H31NO6

MW

441.2515 12-0-Acetyl-1,19-dehydrolucidusculine

C26H35NO5

MW

443.2672 12-0-Acetyllucidusculine 12-0,22-A^-Diacetylatidinc 1,15-O-Diacetylluciculine Spiramine E

C26H37NO5

MW

444.3141 2^raconine

C30H40N2O

MW

445.1889 13-Dehydrocardiopetainine 15-Dehydrocardiopetaiiiine

C„H„NO,

MW

445.2464 Yesoxine

C25H35NO6

MW

447.2046 Cardiopetamine

C27H29NOJ

MW

449.2202 Hypognavine Ignavine Torokonine (Gomando Base I)

C27H31NO5


31

MW

455.2308 9,19-O-Diacetylacsinatine 2,11,13-Tri-O-acetyJhetisine Venudelphine

C26H33NO5

MW

457.2464 1 l-6>-Acetylcardionine Guan Fu Base F

C26H35NO6

MW

459.2410 Palmasine

C29H33NO4

MW

459.2621 Anopteryl-12a-tilgate (1 la-E)estigloylanopterine) 1 la-Destigloylanopterine (Anopteryl-12a-tilgate)

C26H37NO6

MW

460.3090 Zeraconine-iV-oxide

C30H40N2O2

MW

465.2151 Sadosine

C27H3,N06

MW

469.2464 Contorsine(2-C7-Acetyl-3-isobutyrylhetidine)

C27H35NO6

MW

471.2257 Guan Fu Base G 2,11,13-0-Triacetylvakhmatine 1,2,19-Triacety Iseptcntriosine

C26H33NO7

MW

474.3246 Coryphine

C3,H42N202

MW

475.2359 I l-Acetylisohypognavine 15-C>-Acetylryosenamine Hanamisine

C29H33NO5

MW

477.2645 1 -C7-Acetylacofine

Cj^HôClNO^

MW

483.2621 Contortine(2-AcetyI-3(25)-methyIbutyrylhetidine) Sczukitine

C28H37NO6

MW

485.2414 3,2,13-0-Triacetylvakhmadine

C27H35NO7

32


MW

485.2777 1,12,15-0-Triacetylluciculine

CjgHapNO^

MW

487.1995 15-0-Acetyl-13-dehydrocardiopetamine 13-0-Acetyl-15-dehydrocardiopetamine

C29H29NO6

MW

489.2151 15-(9-Acetylcardiopetaniine

C29H3JNO6

MW

490.3195 Acozerine

C3,H42N203

MW

491.2308 Zeravshanisine

C29H33NO6

MW

492.3352 Coryphidine

C3,H44N203

MW

493.2464 15-Veratroylpseudokobusine

C29H35NO6

MW

497.2777 Lassiocarpine

C29H39NO6

MW

499.2570 AT-Deethyl-N-acetyl-1,12,15-0-triacety Inapelline 6,11-O-Diacetylcardionine (basic) N, 11-0-Diacetylcardioninc (neutral)

C28H37NO7

MW

501.2515 Palmadine

C3,H35N05

MW

503.2308 16,17-Dihydro-15,16-dehydroepiscopal idine Episcopalidine

C30H33NO6

MW

503.2519 Glanduline

C27H37NO8

MW

505.2464 16,17-Dihydroepiscopalidine

C30H35NO6

MW

507.2621 Yesoline

C30H37NO6

MW

511.2570 6,13-0-Diacetylgeyerinc

C29H37NO7


33

MW

511.2934 2-0-Acetyl-3-hexahy drobenzoy 1-16,17dihydrohetidine

C3oH4,N06

MW

513.2363 2,11,13,19-0-Tetracetylvakhmatine 2,11,13,14-c^-Tetraacetyltangutisine

CjgHjjNOg

MW

517.2464 1,7.-0-Diacetylcrassicauline B 11,15,-0-Diacetylisohypognavine

C31H35NO5

MW

519.2859 Andersobine- 19-p-^,MDimethylaminobenzoate

C3,H39N205

MW

521.2566 11,15-0-Dibenzoylkobusinc

C34H35NO4

MW

529.2676 13-Acetyl-9-deoxyglanduline 14-Acety1-9-deoxyglanduline

C29H39NO8

MW

531.2257 13-£)ehydropanlculatine 13,15-6-Diacetylcardiopetamine

C31H33NO7

MW

533.2413 Contorine(2-0-Acetyl-3-anisoylhetidine) Cossonine Paniculatine Tadzhaconine

C3,H35N07

MW

536.1840 N, 6-hydroxyepiscopalidine chloride

C3oH3,ClN06

MW

537.2515 6,11-O-Dibenzoylpseudokobusine 6,15-Dibenzoylpseudokobusine

C34H35NO5

MW

541.3040 Anopterine (Anopteryl-11,12-ditiglatc)

C31H43NO7

MW

545.2625 13-0-Acetylglanduline

C29H39NO9

MW

549.2361 2-Desmethylbutyrylcardiopine

C3JH35NO8

34


MW

557.2413 3-E)ehydro-1 -desacetoxy-1,2-dehydrocardiopinine

C33H35NO,

MW

557.2989 7P-Hydroxyanoptcrine(7P-Hydroxyanopterylll(x,12a-ditiglate)

C3,H43N08

7-P-Hydroxyanopteryl-l l a , 12a-ditilgate MW

561.2363 C32H35NO8 AMDesmethyl N, 6-j^co-6-hydroxyepiscopalidine-6cathylate

MW

571.2781 11,13-0-diacctyl-9-deoxyglandulinc

C3,H4,N09

MW

573.2938 4', 7p-Dihydroxyanopterine (7P-Hydroxyanopteryl-11 a-(E)-4'-hydroxy-2'methylbut-2'-enoate 12a-tiglate) 7P-Hydroxyanopteryl-11 a(E)-4'-hydroxy-2'methylbut-2'-enoate 12a-tilgate

C3,H43N09

MW

577.2312 Barbisine 15-Deacty 1 vakognavine

C32H35NO9

MW

579.2832 Anopetryl-11 a-4*-hydroxybenzoate-12a-tilgate lla-Benzoyl-7p-hydroxy 11adestigloylanopterine(7P-Hydroxyanoptcryl1 la-benzoate-12a-tiglate)

C33H41NO8

MW

577.3978 3-E>ehy dro-1 -desacetoxy-1,2-dehy drocardiopine

C33H55NO7

MW

590.4236 Staphimine

C4,H54N20

MW

595.2781 C33H4JNO9 7P-Hydroxy anoptery 1-11 a-(4' -hydroxy )-benzoate12a-tilgate

MW

606.4549 Staphidine

C42H58N2O


35

MW

619.2417 Vaicognavine 11-O-Acetylbarbisine

C34H37NO10

MW

620.4342 Staphinine Staphirine

C42H56N2O2

MW

621.2938 2-Dehydrocardiopimine

C35H43NO9

MW

623.3094 Cardiopimine Cardiopinine

C35H45NO9

MW

633.2938 Cardiopidine Cardiopine

C36H43NO9

MW

635.2367 Barbaline

C34H37NO11

MW

636.4655 Staphisagrine Staphisine

C43H60N2O2

MW

650.4447 Staphigine

C43H58N2O3

MW

650.4811 Staphisagnine

C44H62N2O2

MW

667.3356 3 -O-Acety Icardiopinine

C37H49NO10

MW

668.4917 Pukeensine

C44H64N2O3

MW

675.3043 3-0-Acetylcardiopine

C38H45NO10

MW

676.2394 7-O-Acetylbarbaline

C36H38NO|2

B^. Joshi, S.W. Pelletier and S.K. Srivastava

36 MW

691.2993 Caidiodine

C38H45NOn

MW

741.2785 Delgtandine

C41H43NO12

MW

768.3020 7-0-Acetyldelgrandine

C43H45NO13

MW

790.4556 Tangirine

C49H62N2O7


5.

Occurrence of Diterpenoid Alkaloids in Plant Species

Aconitella stenocarpa (Hossain and P. H. Davis) Sojak. Syn. Consolida Stenocarpa Hossain and PH Davis Stenocarpine Aconitum alboviolaceum Kom. Albovionitine Aconitum anglicum Stapf. 15-0-Acetylcardiopetamine 15-0-Acetyl-13-dehydrocardiopetamine Cardiopetamine Aconitum baicalense Turcz. ex Rapaics {Aconitum czekanovaskyi Steinb) 12-cp/-NapeIline 12-e/7/-Napelline-^-oxide Aconitum barbatum Pers. 11 -O-Acetyl-1,19-dehydrodenudatine Songoramine Songorine (Napellonine, Shimoburo Base I, BuUetine G) Songorine-^-oxide Aconitum bullatifolium var. homotorichum Guan Fu Base A Guan Fu Base G Guan Fu Base Y (Acorine) Aconitum carmichaeli Debeaux Chuaniimine Ignavine Songorine (Napellonine, Shimoburo Base I, Bulletme G) Aconitum contortum Finet et Gagnep Contorine(2-0-Acetyl-3-anisoyIhetidine) Contorsine(2-0-Acetyl-3-isobutyrylhetidine) Contortine(2-Acetyl-3-(2S)-methylbutyrylhetidine) Episcopalidine Aconitum crassicaule Crassicauline B Aconitum czekanovskyi Steinb. Luciculine (Napelline) 12-epi-Napelline 12-epi-Napelline-iVôxide Aconitum delphinifolium DC 13-0-Acety Igomandonine Dictyzine (Dictysine) Gomandonine Yesoxine Aconitum episcopate Levi. 2-Deacetylheterophylloidine

37

^^


Episcopalidine Aconitumfinetianum Hand-Mazz Finetianine Nominine (11-Deoxykobusine, Nomibase-1) Aconitum flavum Hand-Mazz 12-0-Acetyllucidusculine 1,19-Dehydronapelline (1,19-Dehydroluciculine) Flavadine Flavamine Luciculine (Napelline) Lucidusculine (15-0-Acetylnapelline) l-e/7/-Napelline 12-e/7i-Napelline Aconitum gigas Lev et Van. {Lycoctonum gigas Nakai) Atisine Aconitum heterophylloides Stapf. Atisine Heterophylloidine (Panicutine) Aconitum heterophyllum Wall. Atidine Atisine Dihydroatisine Hetidine Hetisine Hetisine-2-one Isoatisine Aconitum ibukiense Nakai 9-Hydroxynominine Ignavine Ryosenamine Ryosenaminol Aconitum japonicum Thunb. 11-O-Acetylisohypognavine 11,15-0-Diacetylisohypognavine Ignavine Isohypognavine Kobusine Sadosine Songorine (Napellonine, Shimoburo Base 1, Bulletine G) Subdesculine Aconitum Japonicum var. montanum Nakai 3-e/7/-Ignavinol Kobusine Aconitum Jinyangense W. T. Wang Denudatine Jyosine (l5-0-Acetyldenudatine)

Carbon-13 and Proton NMR Shift Assignments Aconitum karakolicum Rapaics 12-0-Acety Inapeliine 12-O-Acety lnapelline-A/-oxide Acofine Dihydrosongorine Luciculine (Napalline) 12-e/7i-Napelline Nappelline A^-oxide Songoramine Songorine (Napellonine, Shimoburo Base I, Bulletine G) Aconitum kihneme Nakai Kirinine B Kirinine C Aconitum kojimae Ohwi var. lassiocarpum Tamura Lassiocarpine Aconitum komarovii Steinb. Guan Fu Base Y Guan Fu Base Z Aconitum koreanum (Levi.) Rapaics {A. coreanum) (Syn. A. komarovii Steinb.) Acoridine Coryphidine Coryphine Guan Fu Base A Guan Fu Base F Guan Fu Base G Guan Fu Base Y (Acorine) Guan Fu Base Z Isoatisine Aconitum kusnezoffii Reichb. Denudatine Lepenine Aconitum leucostomum Vorosch. 11-O-Acetyllepenine Acsinatine 9,19-O-Diacetylacsinatine Lepenine Songorine (Napellonine, Shimoburo Base I, Bulletine G) Aconitum liangshanium W. Z. Wang 12-6/7/-1,19 Dehydrolucidusculine 1 l-epi' 1,19-Dehy dronapelline Liangshanine Liangshanone 12-ep/-Lucidusculine 12-€fp/-Napelline Aconitum lucidusculum Nakai Lucidusculine (15-O-Acetylnapelline)

39

40


Aconitum majimaii Nakai Isohypognavine Aconitum miyabei Nakai Miyaconitine Miyaconitinone Aconitum monticola Steinb. A^Desethylsongoramine (Norsongoramine) Norsongoramine Norsongorine Songoiamine Songorine (Napellonine, Shimoburo Base I, Bulletine G) Songorine-Moxide Aconitum nagarum var. lasiandrum W. T. Wang Songoramine Songorine (Napellonine, Shimoburo Base I, Bulletine G) Aconitum napellus (fed on Aphids Brachycaudus aconitici) 12-epi' 1,19-DehydronapeIline 12-e/?/-Napelline Aconitum napellus L. S. Str. (Syn. A. anglicum Stapf.) 15-0-Acety Icardiopetamine 15-0-Acetyl-13-dehydrocardiopetamine Cardiopetamine Luciculine (Napelline) Songoramine Aconitum napellus L. ssp. castellanum J. Molero et C. Blanche 12-c'p/-0-Acetyl-1,19-dehydronapelline 12-6/7/-1,19Dehydronapelline Songoramine Aconitum nasatum Fisch. Ex Reichb. Pseudokobusine Aconitum orientale Mill Acorientine Orientinine Aconitum palmatum Don Atisine 15-Deacety Ivakognavine Hetidine Hetisine Isoatisine Palmadine Paimasine 2,3,13-(9-Triacetylvakhmadine Vakhmadine Vakhmatine Vakognavine Aconitum paniculatum Lam.

Carboii-13 and Proton NMR Shift Assignments Heterophylloidine (Panicutine) Panicudine Paniculamine Paniculatine Aconitumpseudohuiliense, Cheng et Wang Lepedine Lepenine Aconitum pukeense W. T. Wang Pukeensine Aconitum sanyoense Nakai Hanamisine Hypognavine Ignavine Nominine (11-Deoxykobusine, Nomibase-1) Sanyonamine Aconitum sanyoense var. tonense Nakai Hanamisine Sanyonamine Aconitum sczukinii Turez Sczukidine Sczukinine Sczukitine Aconitum septentrionale Koelle (Syn. Aconitum lycoctonum) 2-0-Acetylseptentriosinc Septatisine (Septedinine) Septedine Septenine Septentriosine Aconitum soongaricum stapf. Songorine (Napellonine, Shimoburo Base I, Bulletine G) Aconitum species Ignavine Sadosine Aconitum subcuneatum Nakai Gomandonine Torokonine (Gomando Base I) Aconitum talassicum M. Pop Kobusine Talassamine Talassimidine Talassimine Talatisine Aconitum tanguticum Tangirine Tangutisine Aconitum turczaninowii

41

42


Tupelline Aconitum vilmorrianum Kom Vilmonianone Aconitum yesoense Nakai I -O-Acety llucicuUne Luciculine (Napelline) Aconitum yesoeme var. macroyesoense (Nakai) Tamura 12-0-Acetyl-1,19-dehy drolucidusculine 1 -O-Acetylluciculine 12-0-Acety llucidusculine 15-Benzoy Ipseudokobusine iV-Deethy 1-1,19-dehy drolucidusculine 1,19-Dehydrolucidusculine 1,19-Dehydronapelline (1,19-DehydrolucicuUne) Flavadine Kobusine Lucidusculine (15-0-Acetylnapelline) Pseudokobusine 15-Veratroylpseudokobusine Ycsodine Yesoline Yesonine Yesoxine Aconitum zeravschanicum Steinb. Acozerine Atisine Isoatisine Luciculine (Napelline) Nominine (11-Deoxykobusine, Nomibase-1) Tadzhaconine Zeraconine Zeraconine-iV-oxide Zeravshanisine Anopterus glandulosus Labill. Anopterine (Anopteryl-11,12-ditiglate) Anopteryl I2a-tiglate (lla-Destigloylanopterine) 1 la-Benzoyl-7a-hydroxy-l la-destigloylanopterine (7PHydroxy anopteryl-11 a-benzoate-12a-tiglate) ll-a-Destigloylanopterine (Anopteryl I2a-tiglate) 4',7P-Dihdryoxyanopterine (7p-Hydroxyanoptery 1-11 a-(£)-4'-hydroxy-2*niethylbut-2'-enoate 12a-tiglate) 7P-Hydroxyanopterine (7P-Hydroxyanopteryl-l la,12a-ditiglate) 7-P-Hydroxy anopteryl 1 la,12a-ditiglate Anopterus macleayanus F. Muell. Anopterimine

Carbon-13 and Proton NMR Shift Assignments Anopterimine Aôxide Anopterine (Anopteryl-11,12-ditiglate) Anopteryl lla-4'-hydroxybenzoate 12a-tiglate Anopteryl 12a-tiglate (lla-Destigloylanopterine) 1 la-Benzoyl-7a-hydroxy-l la-destigloylanopterine (7PHydroxyanoptery I-11 a-benzoate-12a-tiglate) 11-a-DestigloyIanopterine (Anopteryl 12a-tiglate) 4',7p-Dihdryoxyanopterine (7P-Hydroxyanopteryl-11 a-(E)-4'-hydroxy-2'methylbut-2*-enoate 12a-tiglate) 7p-Hydroxyanopterine (7p-Hydroxyanopteryl-l la,12a-ditiglate) 7-P-Hydroxy anopteryl-11 a, 12a-ditiglate 7P-Hydroxyanopteryl-lla (4'-hydroxy) benzoate-12a-tiglate 7-p-Hydroxyanoptery 1-11 a-(E)-4'-hydroxy-2'-methylbut-2'-enoate 12atiglate Cocculus laurifolius DC Garryfoline (Laurifoline) Comolida ambigua L. Syn. D, ajacis Ajaconine Dihydroajaconine Consolida axilliflora (DC) Schr6d. (Syn. Delphinium axilliflorum DC.) Ajaconine Hetisine Consolida glandulosa (Boiss. et Huet.) Bomm. (Syn. Delphinium glandularum Boiss et Huett) 13-0-Acetyl-9-deoxyglanduline 14-0-Acetyl-9-deoxy glanduline 13-O-AcetylglanduIine 11,13-O-Diacety 1-9-deoxy glanduline Glanduline Consolida hellespontica (Boiss). Chellespontine Consolida stenocarpa Hussain and P.H. Davis Stenocarpine Delphinium ajacis Ajaconine Dihydroajaconine Delphinium alhiflorum DC 2-Deacetylheterophylloidine Delphinium andersonii Gray Andersobine Delphinium axilliflorum DC Ajaconine Hetisine Delphinium barbeyi (Huth) Huth Barbaline

43

44

BS. Joshi, S.W. Pelletier and S.K. Srivastava

Barbisine Delbidine Geyeridine Delphinium hrunonianum Royle Ajaconine Brunonine Dictyzine (Dictysine) Delphinium cardiopetalum DC (Syn. D, verdunense Balbis) 11-0-Acetylcardionine 15-0-Acety Icardiopetamine 13-C>-Acetylhetisine-2-one Cardiodine Cardionidine Cardionine Cardiopetamine Cardiopidine Cardiopimine Cardiopine Cardiopinine Cossonidine Hetisine-2-one Delphinium carolinianum Walt Ajaconine Delphinium corumbosum Regel Dictyzine (Dictysine) Delphinium cossnianum Batt. Cossonidine Cossonine Delphinium delavayi Franch var. pogonanthum (Hand-Mazz.) Wang Ajaconine Hetisine Hetisine-2-one Delphinium denudatum Wall Delnudine Denudatine Hetisine-2-one Vilmorrianone Delphinium dictyocarpum DC Dictyzine (Dictysine) Dictyzineacetonide Delphinium elatum Ajaconine Delphinium elatum L. cv. pacific giant Delatisine Delphinium fissum Waldst. and Kit ssp. anatolicum Chaudhuri and Davis Delfissinol

Carbon-ia and Proton NMR Shift Assignments Fissiunine Delphinium geyeri Greene Geyeridine Geyerine Geyerinine Delphinium glandulosum Boiss et Huet. 13-0-Acetyl-9-deoxyglanduline 14-0-Acety I-9-deoxyglanduline 13-0-Acetylglanduline 11,13-0-Diacetyl-9-deoxyglanduline Glanduline Delphinium gracile DC 1 l-O-Acetylcardionine 13-0-Acetylhetisine-2-one Cardionine Cardiopetamine Hetisine-2-one Delphinium grandiflorum L 7-0-Acetylgrandine Delgrandine Delphinium macrocentrum Oliv. 13-0-Acetylhetisine Macrocentrine Delphinium nudicaule Torr and Grey Hetisine-2-one Delphinium nudicaule Torr and Grey Hetisine Delphinium nuttalianum Pritz. 13-O-Acetylhetisine Delnuttaline Delnuttidine Delnuttine Hetisine Delphinium occidentale (S. Wats) S. Wats Deibidine Hetisine Hetisine-2-one Delphinium peregrinum var. elongatum Boiss 13-0-Acetylhetisine-2-one Delphinium staphisagria Staphidine Staphigine Staphimine Staphinine Staphirine Staphisagnine

45

^^


Staphisagrine Staphisine Delphinium tamarae Kem. Nath. A^-Desethylsongoramine (Norsongoramine) Norsongoramine Delphinium tatsienense Franch Ajaconine Dictyzine (Dictysine) Hetisine Hetisine-2-one Tatsirine Delphinium uncinatum Hook f. and Thomas Uncinatine Delphinium venulosum Boiss. Hetisine Venudelphine Venulol Venuluson Delphinium verdunense Balbis. 13-0-Acetylhetisine-2-one Delphinium virescens Nutt. Ajaconine Ganya laurifolia Hartw. Cuachichicine Garryfoline (Laurifoline) Isocuauchichicine Isogarryfoline Garrya ovata var. Lindheimeri Torr Cuauchichicine Garryfoline (Laurifoline) Lindheimerine Ovatine Garrya veatchii Kellog Garryine Veatchine Lycotonum gigas Nakai Atisine Spiraea japonica L. fil Spiradine A Spiradine B Spiradine C Spiradine D Spiradine F Spiradine G Spiraea japonica L. fil var. acuminata Spiramine A

Carbon-13 and Proton NMR Shift Assignments Spiramine B Spiramine C Spiramine D Spiramine E Spiramine F Spiramine G Spiramine H Spiramine I Spiramine J Spiramine K Spiramine L Spiramine M Spiraea Japonica L. fil varfortunei (Planchon) Rehd Spiradine A Spiramine B Spiramine C Spiramine D Spirasine I Spirasine II Spirasine III Spirasine IV Spirasine V Spirasine VI Spirasine VII Spirasine VIII Spirasine IX Spirasine X Spirasine XI Spirasine XII Spirasine XIII Spirasine XIV Spirasine XV Spiredine Spiraea Japonica var. incisa Yu Spiramine P Spiramine Q Spiramine R Thalictrum sessile Hayata Spiradine A Spirasine I Spirasine II Spirasine III Spiredine Thalicsessine Thalicsiline

47

48


6. Catalogue of Spectral Data and Physical Constants of Naturally Occurring Diterpenoid Alkaloids and their Derivatives

l-O-ACETYLACOFINE CI

C27H40CINO4

Prepared from acofine 'H N M R : 5 0.64 (3H, 5, H-IS), 1.00 (3H, /, J=7 Hz, H-22), 1.35, 1.40, 1.44 (each 3H, s, Me), 2.00 (3H, s, OAc), 3.26 (IH, bw), 3.85 (IH, bw), 5.05 (IH, ^.Ji=10Hz,J2=7Hz,H.lp).

B Tashkhodzhaev, MN Sultankhodzhaev and IM Yusupova, Khim, Prir, Soedin., 267 (1993).


49

15.O-ACETYLATISINE-Ar,20-AZOMETHINE C22H3iN02;mp 144-148° [a]D-60° *" OAc

1,2

Prepared from atisine

^^C Chemical Shift Assignments^

1. 2. 3.

C-1

42.4

C-12

35.9

C-2

20.0

C-13

25.8

€-3

34.1

C-14

25.0

C-4

32.9

C-15

76.2

C-5

47.0

C-16

151.1

C-6

19.4

C-17

110.1

C-7

31.2

C-18

25.8

C-8

36.7

C-19

60.7

C-9

39.2

C-20

165.1

C-10

42.5

COCH3

170.8

C-11

28.0

COCH3

21.2

SW Pelletier and PC Parthasarathy, J, Am. Chem, Soc, 87,777 (1965). D Dvomik and OE Edwards, Can. J. Chem., 35,860 (1957). NV Mody and SW Pelletier, Tetrahedron, 34,2421 (1978).

B^. Joshi, S.W. Pelletier and S.K. Srivastava

50 7-0-ACETYLBARBALINE

C36H3»NOi2; MW: [M-Hf 676.2368; mp237° Preparedfrombarbaline 'H NMR (CDCI3): 8 1.12 (3H. s, H-18), 1.96 (3H, s, OAc-3), 2.05 (3H, s, OAc1), 2.12 (3H, s, OAc-11), 2.18 (3H, s, OAc-7), 2.29 (IH, brd, J=18 Hz, H-15), 2.35 (IH, s, H-5), 2.47 (3H, s, N-Me), 2.64 (IH, dl, J=18, 1.5 Hz, H-15), 2.83 (IH, d, J=2 Hz, H-12), 2.88 (IH. hid, J=4 Hz, H-14). 2.89 (IH, dd, J=4,9.5 Hz, H-9), 3.06 (IH, brJ, J=4 Hz, H-6), 3.81 (IH, s, H-20), 4.95 (IH, bw, H-17), 5.05 (IH, brt, J=1.5 Hz, H-17), 5.12 (IH, d, J=4 Hz, H-7e,), 5.23 (IH, d, J=3.9 Hz, H-3„), 5.46 (IH, hidd, J=9.5, 2 Hz, H-11„), 5.57 (IH, d J=4.2 Hz, H-U,), 6.09 (IH, t. J=4.2, 3.9 Hz, H-2), 7.55,7.62,7.88 (5H, each m, Ar-H), 9.81 (IH, bw, H-19). C-1

72.3

'^C Chemical Shift Assignments 70.7 C-1' C-U

C-2

66.6

C-12

59.8

C-2', 6'

129.8

C-3

71.8

C-13

205.3

C-3', 5'

128.8

C-4

49.8

C-14

54.1

C-4'

133.7

C-5

58.4

C-15

29.8

N-CH3

33.6

C-6

60.1

C-16

136.0

ArCO

164.9

C-7

69.1

C-17

114.3

COCH3-I

169.1\20.9''

C-8

48.4

C-18

23.5

COCH3-3

170.2,20.6

C-9

49.2

C-19

195.0

COCH3-7

169.6,20.3

C-10

56.6

C-20

66.0

COCH3-II

170.6\21.0''

129.1

****Assignments may be interchanged.

GD Manners, RY Wang, M Benson, MH Ralphs and JA Pfister, Phytochemistry, 42, 875 (1996).


51

11 -O-ACETYLB ARBISINE C34H37NO10; MW: [M+Hf 620; mp SlOBlS^Cdec.)

.t^t

[a]D~57.1°(CHCl3) Prepared from barbisine *H NMR (CDCh): 6 1.10 (5, H-18), 2.00, 2.01,2.11 (each 3H, s, OAc), 2.48 (3H, 5, A^Me), 3.43 (in, d, J=4.5 Hz; H-9p), 3.70 (IH, 5, H-20), 4.78 (IH, d, J=4.5 Hz, H-ll^), 4.86-5.04 (3H, m, H-7p, H-17,), 5.11 (IH, d, J=3.1 Hz, H-l„), 5.38 (IH, q, J=3.1 Hz, H2p). ^^C Chemical Shift Assignments

C-1

68.5

C-ll

65.6

C-20

67.6

56.5 .

N-Me

35.0

C-2

67.8

C-12

C.3

29.5

C-13

206.9

COCH3

169.0,168.6,165.1

C-4

43.6

C-14

50.8

COCH3

20.9,20.8,20.5

C-5

57.5

C-15

28.8

ArCO

165.1

C-6

61.2

C-16

135.0

c-r

129.5

C-7

73.9

C-17

115.4

C-2', 6'

129.5

C.3', 5'

128.6

C.4'

133.3

C-8

47.0

C-18

26.0

C-9

56.4

C-19

193.1

C-10

53.5

P Kulanthaivel, E Holt, J Olsen and SW Pelletier, Phytochemistry, 29,293 (1990).

52


11-0-ACETYLCARDIONINE CzfiHjjNOe; MW: 457.2463

21 22 OCOCH

\

23 /^^

24

[ a b - S J l " (CHCb) Delphinium cardiopetalum, DC; D. gracile, DC.

'H NMR (CDClj): 8 1.20 (6H, d, J=7 Hz, H-23, H-24), 1.33 (3H, s, H-18), 1.56 (IH, s, H-5), 1.65 (IH, d, J=2 Hz, H-9), 2.04 (3H, s, OAc), 2.32 (IH, brd, J=10.8 Hz, W|/2=7.5 Hz, H-14), 2.37 (IH, d, J=12.2 Hz, H-19J, 2.59 (IH, s, H-20), 2.63 (IH, sept, J=7 Hz, H-22), 3.08 (IH, d, J=12.2 Hz, H-19B), 4.99 (IH, s. H-UJ, 5.01, 5.34 (each IH, d, J=2.5 Hz, H-17). 5.68 (IH, t. J=2.2 Hz, H-15B). Me OH

"C Chemical Shift Assignments (CDClj) C-1

35.6

C-14

40.9

C-2

19.4

C-15

71.1

C-3

27.7

C-16

148.0

C-4

38.2

C-17

109.4

C-5

61.3

C-18

30.6

C-6

99.0

C-19

60.3

C-7

39.6

C-20

73.4

C-8

45.8

C-21

177.1

C-9

56.3

C-22

34.3

C-10

50.4

C-23

19.2

C-11

76.3

C-24

19.3

C-12

73.1

COCH3

172.2

C-13

36.2

COCH3

21.4

G de la Fuente, JA Gavin, M Reina and RD Acosta, J. Org. Chem., 55,342 (1990).


53

15-O-ACETYLCARDIOPETAMINE H0\

./i-lo.J

C29H3,N06^MW: 489'-';mp236-237°'' [a]D+16°', [a]D+ 12° (EtOH)^ Aconitum napellus L. S. Str. (syn. A. anglicum Stapf.) ; Delphinium cardiopetalum DCl 'H N M R (CDCI3)': 5 1.10 (3H, s, H-18), 1.82 (2H, m, H-7), 2.02 (IH, ;r, H-5), 2.10 (3H, s, OAc), 2.22 (IH, d, J=12 Hz, H-19B),

2.28 (IH, d, J=13.3 Hz, H-U), 2.29 (IH, rf. J=10 Hz, H-14), 2.58 (IH, d, J=2.5 Hz, H-12), 3.37 (IH, bra, Wi/2=6 Hz, H-6), 3.48 (IH, d, J=13.2 Hz, H-IJ, 4.18 (IH, brrf, J=9.7 Hz, W,/2=6 Hz, H-13), 5.15 (IH, s. H-15), 5.26, 5.34 (each IH, s, H-17), 5.57 (IH, d. 3=9 Hz, H-11), 7.42,8.08 (5H, each m, Ar-H). C-1

'^C Chemical Shift Assignment^ C-15 44.1

72.0

C-2

212.0

C-16

144.7

C-3

50.0

C-17

116.5

C-4

42.6

C-18

28.6

C-5

60.2

C-19

64.6

C-6

65.2

C-20

70.1

C-7

32.9

ArCO

166.6

C-8

48.1

c-r

129.8

C-9

49.4*

C.2',6'

129.8

C-10

55.0

C-3', 5'

129.7

C-11

75.1

C-4'

133.3

C-12

47.8

COCH3

171.0

C-13

69.6

COCH3

21.3

C-14

49.6*

"Assignments may be interchanged. 1. 2. 3.

G de la Fuente, M Reina and E Valencia, Heterocycles, 29,1577, (1989). AG Gonzdlez, G de la Fuente, M Reina, PG Jones and PR Raithby, Tetrahedron le//., 24,3765 (1983). AG Gonzdlez, G de la Fuente, M Reina, R Diaz and I Timdn, Phytochemistry, 25, 1971 (1986).


54 3-(?-ACETYL CARDIOPINE

C38H45NO10; amorphous; MW 675 Prepared from cardiopine ^H NMR (CDCI3): 8 0.57 (H, u J=7.4 Hz, H-4'), 0.88 (H, d, J=7.0 Hz, H.5'), 1.04 (3H, s, H-18), 1.73 (IH, dd, J=13.6, 2.6 Me Hz, H-7p), 2.04 (3H, 5, OAc), 1.89, 1.96 5' AcO (6H, 5, OAc, 2.31 (IH, 5, H-5), 2.22 (IH, brd]^n Hz H.15„), 2.53 (IH, d, J=12.8 Hz, H-19p), 2.37 (IH, d, J=9.9 Hz, H-12), 2.37 (lH,/w, H-15p), 2.63 (IH, dd, J=10.1 Hz, H-14), 3.29 (IH, d, J=12.8 Hz, H-19J, 3.46 (IH, bw, 3.46 W,/2=6.2Hz, H-6), 3.85 (IH, 5, H-20), 5.11 (IH, d, J=4.8 Hz, H-3p), 4.86 (IH, br^, H-17e), 4.99 (IH, bw, H-17z), 5.43 (IH, d, J=9.4 Hz, H-llp), 5.52 (IH, dt, J=9.9, 2.6 Hz, H-13p), 5.69 (IH, dd, J=3.2, 4.3 Hz, H-2p), 6.09 (IH, d, J=3.0 Hz, H-1 J, 7.46 (2H, r, J=7.8 Hz, Ar-H), 7.57 (2H, r, J=7.1 Hz, Ar-H), 8.11 (IH, ^, J=7.2 Hz, Ar-H).

4* 3* 2* r MeCHaCHCCXD*

'^C Chemical Shift Assignments

c-r

174.4

C-2'

39.5

73.3

C-3'

25.0

C-14

49.1

C.4'

10.7

58.9

C-15

33.6

C-5'

15.7

C-6

63.5

C-16

141.5

COCH3 170.0(1), 169.9(3), 171.0(11)

C-7

35.2

C-17

110.6

COCH3

C-8

44.1

C-18

25.1

ArCO

165.9

C-9

51.5

C-19

58.8

C-l"

129.8

C-1

72.3

C-ll

75.0

C-2

65.7

C-12

46.4

C-3

70.8

C-13

C-4

41.3

C-5

C-10 54.1

C-20 . 65.7

21.2(1), 20.6 (3), 21.4 (11)

C.2",6" 129.6 C-3", 5" 128.8 C-4''

133.1

M Reina, A Madinaveitia, JA Gavfn, and G de la Fuente, Phytochemistry, 41,1235 (1996).


55

3-aACETYL CARDIOPININE 3" 2"

4 . . / " y : QOCK ^

\ y

C37H43NO,o; amorphous; MW 661

^ A r> J^*^ ^CHa

^^l

^..JLi

J

Prepared from cardiopininc

'H NMR (CDCh): 5 0.10 (IH, d, J=3Hz, H-

2' C H C O O ^ . . . ^ A < L X * X y ^ I Me I N—]--. 4' ^.-U ^ ^ J ^ : ^ AcO' .'T^ ^ ^ ' ' ^Me

12), 5.71 (Ih, dd, J-5,3 Hz, HzP), 5.10 (IH, d. J-Sllz, H-3P), 2.30 (IH, 5, H-5), 3.61 (IH, brs, wl/2 6.2 Hz, H-6), 1.74 (IH, dd, J=14, 2.3 Hz, H-7),2.42(IH.m,H.9),5.45(lH,J,J=9.6Hz, "-^ ^p)' -•'•2 (HI,

Alkaloids: Chemical and Biological Perspectives

Alkaloids: Chemical and Biological Perspectives

Alkaloids: Chemical and Biological Perspectives (Vol. 10)