Table Of ContentReactivity and Structure
Concepts in Organic Chemistry
Volume 26
Editors:
Klaus Hafner Jean-Marie Lehn
Charles W. Rees P. von Rague Schleyer
Barry M. Trost Rudolf Zahradnik
Leo A. Paquette· Annette M. Doherty
Po lyquinane
Chemistry
Syntheses and Reactions
With 140 Schemes
Springer-Verlag
Berlin Heidelberg New York
London Paris Tokyo
Professor Leo A. Paquette
Dr. Annette M. Doherty
Evans Chemical Laboratories
The Ohio State University
Columbus, Ohio 43210/USA
ISBN-13: 978-3-642-72600-2 e-ISBN-13: 978-3-642-72598-2
DOl: 10.1007/978-3-642-72598-2
Library of Congress Cataloging - in - Publication Data
Paquette, Leo A. Polyquinane chemistry. (Reactivity and structure: concepts in organic
chemistry; v. 26) Bibliography: p. Includes index.
1. Quinanes. I. Doherty, Annette M. (Annette Marian), 1961-. II. Title. III. Series:
Reactivity and structure ; v. 26.
QD335-.P33 1987 547' .593 87-9471
ISBN-13: 978-3-642-72600-2 (U.S.)
This work is subject to copyright. All rights are reserved, whether the whole or part of the
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copyright fee must always be paid. Violations fall under the prosecution act of the German
Copyright Law.
© by Springer-Verlag Berlin Heidelberg 1987
Softcover reprint of the hardcover 1st edition 1987
The use of registered names, trademarks, etc. in this publication does not imply, even in the
absence of a specific statement, that such names are exempt from the relevant protective
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Typesetting: Friedrich Pustet, Regensburg.
2152/3020·543210
List of Editors
Professor Dr. Klaus Hafner
Institut fur Organische Chemie der TH Darmstadt
Petersenstr. 15, D-6100 Darmstadt
Professor Dr. Jean-Marie Lehn
Institut de Chimie, Universite de Strasbourg
1, rue Blaise Pascal, B.P. 296/R8, F-67008 Strasbourg-Cedex
Professor Dr. Charles W. Rees, F. R. S. Hofmann
Professor of Organic Chemistry, Department of Chemistry
Imperial College of Science and Technology
South Kensington, London SW7 2AY, England
Professor Dr. Paul v. Rague Schleyer
Lehrstuhl fur Organische Chemie der Universitat Erlangen-Nurnberg
Henkestr. 42, D-8520 Erlangen
Professor Barry M. Trost
Department of Chemistry, The University of Wisconsin
1101 University Avenue, Madison, Wisconsin 53 706, U.S.A.
Professor Dr. Rudolf Zahradnik
Tschechoslowakische Akademie der Wissenschaften
J.-HeyrovskY-Institut fur Physikal. Chemie und Elektrochemie
Machova 7, 121 38 Praha 2, C.S.S.R.
Table of Contents
I Introduction.................................
II New Synthetic Developments. 2
A Annulation Reactions .. 2
1 Acid-and Base-Promoted Cyclizations . 2
2 Metal-Promoted Ring Closures. 8
3 Free Radical Processes . . . 10
4 [3 +2 ] Cycloaddition Methodology 12
5 Weiss-Cook Condensations 14
6 Intramolecular Diels-Alder Reactions 15
7 Cyclization of Diazo Compounds .. 16
8 Miscellaneous 17
B Ring Expansion, Contraction, and Cleavage Processes 19
C Pauson-Khand Reaction 24
D Photochemical Approaches . 27
1 Oxa-di-n-methane Entry . 27
2 Meta Olefin Addition to Arenes 30
E Rearrangement Routes to Polyquinanes 34
1 Thermochemical Pathways . 34
2 Cleavage of Cage Molecules 37
3 Carbocation-Based Approaches 41
4 Photochemical Processes . 46
5 Base-Promoted Isomerizations . 48
6 Carbenic and Transition Metal-Catalyzed Schemes . 50
F Trapping of 1 ,3-Diyls . 53
G Transannular Cyclizations .. 55
III Functional Group Manipulation Within Polyquinanes 58
A Reactions Involving Ketonic Substrates. 58
B Carbocationic Processes .. 64
C Reactions Involving Olefinic Centers 67
D Miscellaneous 70
VII
Table of Contents
IV Physical Data for, and Theoretical Analysis of, Polyquinanes . 72
A Crystal Structure Data . . . . 72
B Photoelectron Spectra . . . . 74
C Molecular Orbital Calculations 75
D Miscellaneous ....... . 75
V Molecules of Theoretical Interest . 77
A Pentalene. . . . . . . . . . 77
B Semibullvalenes .. . . . . 78
C Syn/anti-Sesquinorbornenes 81
D Triquinacenes ...... . 85
E Tricyclic [lO]Annulenes. . . 88
F Fenestranes and Related Molecules . 91
G (D3)-Trishomocubanes and Congeners 97
H Peristylanes. . . . . . . . . . . . . . 100
I Chemistry Surrounding Dodecahedrane 104
VI Natural Products Chemistry . . . . . . . . . . . 107
A Isolation and Physical Properties . . . . . . 107
B Biosynthesis and Chemical Transformations 110
VII Synthesis of Nonpolycyclopentanoid Natural Products
by Way ofDiquinane Intermediates 112
A Allamcin .. 112
B Boonein .. 113
C Brefeldin A . 114
D Dendrobine. 114
E Forsythide Aglycone Dimethyl Ester 115
F Ikarugamycin. . . 116
G Iridodial . . . . . . . . 117
H Isoiridomyrmecin. . . . 117
I Loganin and Analogues. 118
J Oplopanone 121
K Plumericin 122
L Trichodiene 123
M Udoteatrial . 124
N Xylomollin . 125
VIII Synthesis of Diquinane Natural Products . . . 127
A Cedranoids . . . . . . . . . . . 127
B The Pentalenolactone Group . . 130
C Quadrone and Terrecyclic Acid . 133
VIII
Table of Contents
D Ptychanolide · .. 141
E Albene ...... 142
F Carbaprostacyclins 144
G Ryanodine and the Ryanoid Insecticides 164
IX Synthesis ofTriquioane Natural Products. 169
A Linear Triquinanes . . . . 169
1 Hirsutene · ...... 169
2 The Capnellene Group . 174
3 Coriolin ..... 182
4 Hirsutic Acid. . . . . . 188
B Angular Triquinanes ... 191
1 Isocomene Sesquiterpenes 191
2 Silphinene · ....... 194
3 Pentalenene and Pentalenic Acid . 195
4 Senoxydene .......... 199
5 Silphiperfolene and Congeners . 202
6 Retigeranic Acid . . 205
C Propellane Structures . 206
1 Modhephene . 206
X References.................................. 209
Subject Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ., 227
IX
I Introduction
New methods for the construction of condensed five-membered ring systems
continue to be developed at an accelerated pace. The challenges underlying this
tremendous current upsurge of interest arise from several directions. One stems
from the desire to elucidate and resolve those special problems associated with
the incorporation of added strain not present when six-membered rings are
mutually fused. The many structurally interesting polyquinane natural products
isolated and characterized in recent years have provided a particularly delightful
forum for application of various new synthetic protocols, many of which must
equally well accommodate the particular stereochemical demands of each indi
vidual target. Synthetic elaboration of a marvellous array of new unnatural
molecules also holds continued fascination.
In the past, we have attempted to keep others abreast of developments in this
rapidly burgeoning area by authoring a pair of comprehensive reviews in Topics
in Current Chemistry that appeared in 1979 [1] and 1984 [2]. During this period,
others have also surveyed the developments in cyclopentannulation [3] and the
cyclopentanoid field in general [4]. In the last couple of years, the pace at which
new synthetic facets have been reported has become more frenetic than ever
before. Accordingly, a suitable updating of the exciting newer findings was
deemed appropriate and the present overview, which extends approximately to
mid - 1986, was written. Once again, our hope is that compilations of this type
will serve to stimulate imaginative new scientific ventures that will propel the field
forward to still greater maturity.
Acknowledgments
In writing a book about recent developments in the chemistry of polyquinane
systems, we are conscious of the very considerable contributions to this subject by
our colleagues throughout the world. In many ways, this book stands as a
testimony to their research accomplishments. In an undertaking of this mag
nitude, especially in view of the large number of illustrations, some errors will be
inevitable. We hope that these do not otherwise detract from the intended impact
of the overall theme.
The enormously ardous tasks of drawing all of the chemical structures and of
typing the entire manuscript were the master work of Mrs. Donna Rothe, to
whom we publicly express our deepest gratitude and appreciation.
II New Synthetic Developments
A Annulation Reactions
1 Acid- and Base-Promoted Cyclizations
Lee and Richardson have disclosed that it is entirely feasible to cyclopentannulate
silyl enol ethers in a one-pot two-step process. For example, condensation of 1
with the readily available stannane 2 in the presence of trimethylsilyl triflate leads
to an adduct that cyclizes to 3 on subsequent exposure to titanium tetrachloride
[5]. This new strategy is notable in that a doubly functionalized product results.
1,2-Bis( trimethylsilyloxy )cyclopentene (4) condenses with chloride 5 in the pres
ence of anhydrous zinc chloride to give a 1:1 mixture of 6 and 7 [6]. The first
relevant point is that alkylation proceeds without annihilation of the allyl silane
moiety. Consequently, this functionality is available for subsequent ring closure
as illustrated by the independent conversion of 6 and 7 to 8 and 9, respectively,
when treated with ethylaluminum dichloride.
cO
..
1.TMSOTf
(51%)
,
2.TiC14 \.
HOMe
d',
,~:o
(J(
0TMS
I + ~TMS ZnCI2 .. ~TMSO~ ~
CH2CI2
OTMS
OOC
CI
o
I
EtAICI2'
toluene. _78oC
~~
60~H H~P
-
8
Jager and his coworkers have developed an intriguing and highly serviceable
iterative cyclopentane annulation of a,~-unsaturated ketones [7]. The process,
2
A Annulation Reactions
which is illustrated in Scheme I, features as its key steps conversion to an allylic
alcohol by hydride reduction or Grignard addition, Claisen rearrangement via
either the ortho ester or ketene acetal modification, and polyphosphoric acid
induced cyclization of the derived carboxylic acid.
COOH
~
CH3CH2COOH "" n-Bu
135-1400C
CH3
1 LiAIH4 !L/Bu
2.Claisen ~COOH
CH3
~ l.LiAIHlOMe)3
""
~
2.C+aisen
o Scheme I
Use of the intramolecular Wadsworth-Emmons reaction for fusing a cyc
lopentenone ring can sometimes prove quite troublesome. Aristoff has demons
trated that avoidance of the use of strong base and substitution of one equivalent
of potassium carbonate and two equivalents of lS-crown-6 in warm toluene may
alleviate this problem [S]. The 70% yield realized in the formation of lOis
apparently indicative of the efficiency of this process. It is widely recognized that
the presence of an angular substituent causes aldolization to proceed less ardu
ously. The cyclization of 11 constitutes an additional example [9].
L
K2C03 ....
18-cr-6
toluene
OTHP OTHP OTHP OTHP
10
tE>=o
30%KOH
~
11
The elusive ketone 12 has been generated by cyclization of a polymer-bound
precursor and liberation under strongly basic conditions [10]. Through use ofthe
three-phase test, 12 was shown to be capable of acting as a diene but not as a
dienophile in select pericyclic reactions.
3
