Table Of Content190
scipoT ni Current Chemistry
Editorial Board
A. de Meijere • K.N. Houk. J.-M. Lehn. S.V. Ley
J. Thiem • B.M. Trost E • V6gtle • H. Yamamoto
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Stereoselective
Heterocyclic
Synthesis II
Volume Editor: .P Metz
With contributions by
W. H. Chan, E Chiu, M. Lautens,
A. W. M. Lee, .P Perlmutter, .S M. Weinreb
r e g n~ i r p S
This series presents critical reviews of the present position and future trends in
modern chemical research. It is addressed to all research and industrial chemists
who wish to keep abreast of advances in the topics covered.
sA rule, a contributions are specially commissioned. The editors and publishers will,
always however, be pleased to suggestions receive and supplementary information.
Papers are accepted for" Topics in Current Chemistry" in English.
In references Topics in Current Chemistry is abbreviated Curr. Chem. Top. and is
cited as a journal.
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Volume Editor
Prof, Dr. Peter Metz
Institut ftir Organische Chemie
Technische Universit~it Dresden
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D-01062 Dresden, Germany
E-mail: metz@cochO l.ch m.tu-dresden.de
Editorial Board
Prof. Dr. Armin de Meijere Prof. K.N. Houk
Institut fiir Organische Chemie Department of Chemistry and Biochemistry
der Georg-August-Universit/it University of California
Tammannstrat]e 2 504 Higard Avenue
77073-D G6ttingen, Germany soL Angeles, AC ,9851-42009 ASU
E-mail: ed.negnitteog-inu@cocu E-mail: ude.alcu.mehc@kuoh
Prof. Jean-Marie Lehn Prof. Steven .V Ley
Institut de Chimie Chemical University Laboratory
de Universit~ Strasbourg Road Lensfield
1 rue Pascal, Blaise .B .P Z 8R/692 2BC WE1 Britain Great Cambridge,
80076-F Strasbourg France Cedex, E-mail: svll .ca.mac.suc@00O uk
E-mail: rf.gbsarts-u.eimihc@nhel
Prof. Dr. Joachim Thiem Prof. Barry M. Trost
Institut Organische fiir Chemie Department of Chemistry
ti~tisrevinU Hamburg Stanford University
Martin-Luther-King-Platz 6 Stanford, AC ,0805-50349 ASU
64102-D Hamburg, Germany E-mail: ude.drofnats.dnalel@tsortmb
[email protected] E-mail:
Pro£ Dr. Fritz V6gtle Prof. Hisashi Yamamoto
Institut fiir Organische Chemie School of Engineering
und Biochemie der ti~tisrevinU University Nagoya
Gerhard-Domagk-St ehtar 1 10-464 Nagoya, Chikusa, Japan
12135-D Bonn, Germany :liam-E pj.ca.u-ayogan.cc.ccun@a88954j
:liam-E ed.nnob-inu.eimehcLeimehcnS@eltgeov
ecaferP
Heterocycles play a central role in organic synthesis. Above all due to the in-
teresting biological activities associated with a large number of these structurally
diverse compounds, many heterocycles have been and will be challenging targets
for total synthesis. Moreover, even if the final goal of a synthesis is not heterocyclic,
at least a central intermediate or a key reagent used along the synthetic sequence
most surely will be. This holds especially true if stereoselectivity is an important
issue, as modern heterocyclic chemistry provides the synthetic organic chemist
with an excellent arsenal of methods and strategies for the stereocontroUedc on-
struction and elaboration (including the cleavage) of heterocycles. Recent years
have witnessed exciting new findings in this field, and it is the aim of this two-
volume set on"Stereoselective Heterocyclic Synthesis" within the series Topics in
Current Chemistry to present a selection of these novel developments.
As the guest editors I am very glad that leading researches in this area havec on-
tributed highly inspiring accounts with up-to-date coverage to this compilation.
Part I features chapters on "Hetero Diels-Alder Reactions in Orgnic Chemistry"
by L.F. Tietze and .G Kettschau describing the state of the art for these useful
[4 + 2] cycloadditions,w hich yield a wide variety of heterocycles and "Tandem
sessecorP of Metallo Carbenoids for the Synthesis of Azapolycycles" by A. Padwa
surveying attractive routes to complex ring systems based upon 1,3-dipolar
cycloadditions. Part II comprises chapter on "Using Ring-Opening Reactions of
Oxabicyclic Compounds as a Strategy in Organic Synthesis" by .2t Chiu and
M.L autens focussing on the preparation and the synthetic utility of the versatile
title compounds, "The Nucleophilic Addition/Ring Closure (NARC) Sequence for
the Stereocontrolled Synthesis of Heterocycles" a powerful tactical combination
disccussed by .P Perlmutter,"Chiral Acetylenic Sulfoxides and Related Compounds
in Organic Synthesis" by A.W..M. Lee and .W .41 Chan emphasizing the use of
sulfur-activated acetylenic and vinyl units for the efficient preparation of
heterocycles, and "N-Sulfonyl Imines - Synthons Useful in Stereoselective Organic
Synthesis" by S.M. Weinreb giving a comprehensive review on the chemistry of
these valuablee lectron-deficient compounds.
I hope that the articles collected in this two-volume set on "Stereoselective
Heterocyclic Synthesis" will not only serve experts in the field but will also
attract the interest of scientists not yet familiar with this fascinating research
topic.
Dresden, March 1997 Peter Metz
elbaT of stnetnoC
Using Ring-Opening Reactions of Oxabicyclic Compounds
as a Strategy in Organic Synthesis
.P Chiu, M. Lautens ..............................
The Nucleophilic Addition/Ring Closure (NARC)
Sequence fort he Stereocontrolled Synthesis of Heterocycles
.P Perlmutter .................................. 87
Chixal Acetylenic Sulfoxides and Related Compounds
in Organic Synthesis
A. .W M. Lee, W. H. Chan ........................... 103
N-Sulfonyl Imines - Useful Synthons in Stereoselective Organic Synthesis
.S M. Weinreb ................................. 131
Author Index Volumes - 151 190 ....................... 185
Table of Contents of Volume 189
Stereoselective I Heterocyclic Synthesis
Volume Editor: P. Metz
Hetero Diels-Alder Reactions in Organic Chemistry
.L E Tietze, G. Kettschau
Tandem Processes of Metallo Carbenoids
for the Synthesis of Azapolycyles
A. Padwa
gnisU Ring-Opening Reactions of cilcycibaxO
sdnuopmoC sa a Strategy ni Organic sisehtnyS
Pauline Chiu 1 and Mark Lautens 2
1 Department of Chemistry, University of Hong Kong, Pokfulam Road, Hong Kong
E-marl: [email protected]
2 Department of Chemistry, University of Toronto, Toronto, Canada SSM 1A1
E-marl: [email protected]
This chapter discusses the various methods for the preparation of oxabicyclic compounds,
with an emphasis on the stereo- and enantioselective synthesis of these substances. Methods
to desymmetrize oxabicyclic compounds are also presented. The utility of these sub~
meso
strates for organic synthesis is demonstrated by the many strategies available for ring-opening
the bicyclic compounds to yield cyclic and acyclic structures. Examples demonstrating how
this strategy has been incorporated into the efficient syntheses of many natural products are
presented.
.sdrowyeK Cycloaddition, oxabicyclic, ring opening, stereocontrol, natural products
Table of Contents
Introduction ............................ 3
Preparation of Oxabicyclic Substrates .............. 4
2.1 Cycloaddition with Furan Derivatives .............. 4
2.1.1 4 + 2 Cycloadditions with Dienophiles ............. 4
2.1.2 4 + 3 Cycloadditions with Oxyallyl Cations ........... 8
2.1.3 4 + 3 Cycloadditions with Allylic Cations ............ 12
2.1.4 4+4 Cycloadditions with Pyrones ................ 13
2.1.5 Cyclopropanation/Rearrangement of Furan Derivatives .... 14
2.2 5 + 2 Cycloadditions of Pyrylium Betaines ........... 15
2.3 Cycloadditions of Cyclic Carbonyl u ............. 18
2.4 Fragmentation of Cyclic Oxonium Intermediates ........ 20
2.5 Annulations of 1,3-Dinucleophiles with
Dicarbonyl Compounds ...................... 21
2.6 Transannular Addition of Nucleophiles .............. 23
2.7 Miscellaneous Reactions ...................... 25
Survey of Functionalization Reactions of Oxabicyclic Substrates 26
3.1 Stereoselectivity of Functionalizations .............. 26
3.1.1 exo/endo Selectivity ......................... 26
3.1.2 Regioselectivity ........................... 30
3:2 Enantioselective Desymmetrization Reactions .......... 32
3.2.1 Desymmetrization of Oxabicyclo2.2.1 Substrates ....... 33
3.2.2 Desymmetrization of Oxabicyclo3.2.1 Substrates ....... 34
scipoT ni tnerruC ,yrtsimehC .loV 091
(cid:14)9 regnirpS galreV nilreB grebledieH 7991
2 E Chiu. .M Lautens
Ring-Opening Reactions of Oxabicyclic Substrates ....... 35
4.1 Cleavage of Carbon-Carbon Bonds in the
Oxabicyclic Framework ....................... 35
4.1.1 Oxidation of the Carbonyl Functionality ............. 35
4.1.2 Oxidative Cleavage ofVicinal Diols in the Carbon Framework 38
4.1.3 Oxidative Cleavage of the Carbon Framework .......... 39
4.1.4 Retro-Dieckmann/Retro-Aldol Reactions ............. 40
4.1.5 Photochemically-Induced Cleavage ................ 41
4.1.6 Electrochemical Cleavage ...................... 42
4.1.7 Acid-Induced Skeletal Rearrangements .............. 42
4.1.8 Miscellaneous Cleavage Reactions ................. 43
4.2 Cleavage of Carbon-Oxygen Bonds in the
Oxabicyclic Framework ....................... 44
4.2.1 Oxygen Bridge Activation by an Electron-Donating Group
at the Bridgehead Carbon ...................... 44
4.2.2 Generation of a Carbanion a to the Carbon-Oxygen Bond . . . 45
4.2.3 Generation of a Carbanion y to the Carbon-Oxygen Bond . . . 48
4.2.4 Heterolytic Cleavage Induced By Acids .............. 49
4.2.4.1 Protic Acids ............................. 49
4.2.4.2 Boron-Based Lewis Acids ...................... 52
4.2.4.3 Silyl Lewis Acids ........................... 54
4.2.4.4 Other Lewis Acids .......................... 55
4.2.5 Grob Fragmentation ......................... 56
4.2.6 Overall Addition of Hydride .................... 56
4.2.6.1 Hydrogen Addition ......................... 56
4.2.6.2 Single Electron Transfer Reductions ................ 57
4.2.6.3 Reductive Elimination ....................... 60
4.2.6.4 Metal Hydride Reductions ..................... 61
4.2.6.4.1 fl-Hydridic Organometallic Reagents ............... 61
4.2.6.4.2 Boranes and Borohydrides ..................... 62
4.2.6.4.3 Aluminum Hydrides ........................ 63
4.2.6.4.4 Tin Hydrides ............................. 67
4.2.6.5 Photochemical Reductions ..................... 68
4.2.7 Overall Addition of Alkyl/Aryl Groups .............. 69
4.2.7.1 Silyl Enol Ether and a Lewis Acid ................. 69
4.2.7.2 Organolithium Reagents ...................... 69
4.2.7.3 Organocuprate Reagents ...................... 75
4.2.7.4 Transition Metal-Catalyzed Alkylative Ring-Opening ...... 77
Conclusions and New Frontiers .................. 78
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
