Strain and Its Implications in Organic Chemistry: Organic Stress and Reactivity

519 Pages·1989·13.119 MB·English

by  Barry M. Trost (auth.), Armin de Meijere, Siegfried Blechert (eds.)

Strain and Its Implications in Organic Chemistry
Organic Stress and Reactivity
NATO ASI Series
Advanced Science Institutes Series
A Series presenting the results of activities sponsored by the NA TO Science Committee,
which aims at the dissemination of advanced scientific and technological knowledge,
with a view to strengthening links between scientific commuflities.
The Series is published by an international board of publishnrs in conjunction with the
NATO Scientific Affairs Division
A Life Sciences Plenum Publishing Corporation
B Physics London and New York
C Mathematical Kluwer Academic Publishers
and Physical Sciences Dordrecht, Boston and London
o Behavioural and Social Sciences
E Applied Sciences
F Computer and Systems Sciences Springer-Verlag
G Ecological Sciences Berlin, Heidelberg, New York, London,
H Celi Biology Paris and Tokyo
Series C: Mathematical and Physical Sciences· Vol. 273
Strain and Its Implications
in Organic Chemistry
Organ ic Stress and Reactivity
edited by
Armin de Meijere
Institut fUr Organische Chemie,
Universitat Hamburg, Hamburg, F.R.G.
and
Siegfried Blechert
Institut fUr Organische Chemie,
Universitat Bonn, Bonn, F.R.G.
Kluwer Academic Publishers
Dordrecht / Boston / London
Published in cooperation with NATO Scientific Affairs Division
Proceedings of the NATO Advanced Research Workshop on
Strain and Its Implications in Organic Chemistry
Organic Stress and Reactivity
Ratzeburg, F.R.G.
28 August - 2 September 1988
Library of Congress Cstaloglng In Publication Data
Strain and Its Implications In organic chellstry : organic stress and
reactivity I edIted by ArmIn de MelJere and SIegfrIed Blechert.
p. CN. -- (NATO ASI serIes. SerIes C, Mathematical and
physical scIences; vol. 273)
·Publlshed In cooperation with NATO ScIentific Affairs Division."
Inc 1u des 1n dex.
1. Chemical bonds--Congresses. 2. Chemistry, Organlc--Synthesls
-Congresses. 3. OrganIc cOlpounds--Congresses. I. Mel Jere, A. de.
II. Blechert, Siegfried, 1946- III. North AtlantIc Treaty
OrganIzatIon. ScIentIfic Affairs DivIsion. IV. SerIes: NATO ASI
serIes. Series C, Mathematical and phYSical sciences; no. 273.
00461 . S875 1989
547.1·39--dc20 89-31035
ISBN-13: 978-94-010-6907-6 e-ISBN-13: 978-94-009-0929-8
001: 10.1007/978-94-009-0929-8
Softcover reprint of the hardcover 1st edition 1989
Published by Kluwer Academic Publishers,
P.O. Box 17, 3300 AA Dordrecht, The Netherlands.
Kluwer Academic Publishers incorporates the publishing programmes of
D. Reidel, Martinus Nijhoff, Dr W. Junk and MTP Press.
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In all other countries, sold and distributed
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printed on acid free paper
All Rights Reserved
© 1989 by Kluwer Academic Publishers
No part of the material protected by this copyright notice may be reproduced or
utilized in any form or by any means, electronic or mechanical, including photo
copying, recording or by any information storage and retrieval system, without written
permission from the copyright owner.
In Memoriam Hans Musso
TABLE OF CONTENTS
Foreword X III
xv
List of Participants
B. M. Trost
Some Synthetic Implications of the Concept of Cyclopropyl Units as Pseudo-Func
tional Groups
K. N. Houk
Stereoselective Electrocyclizations and Sigmatropic Shifts of Strained Rings :
To rquoelectronics ! 25
E. Piers
The Preparation and Thermal Rearrangement of Functionalized 6-(1-Alkenyl)bi
cyclo[3.1.0]hex-2-enes. Applications to Synthesis. 39
*
H. U. Reissig ,R. Zschiesche, A. Wienand, M. Buchert
Synthesis with Donor-Acceptor-Substituted Vinylcyclopropanes 51
*
W. Ando ,N. Tokitoh
Synthesis of Functionalized Episulfides 59
*
L. A. Paquette ,J. Dressel
Through-Bond Interaction via Cyclobutane Relay Orbitals as a Means of Extending
Conjugation 77
*
T. Hudlicky ,A. Fleming, T. Lovelace, G. Seoane, K. Gadamasetti,
G. Sinai-Zingde
[2+3]-Carbo-and Heterocyclic Annulation in the Design of Complex Molecules 109
M. S. Baird*, J. R. AI-Dulayymi, H. H. Hussain
Synthetic and Mechanistic Aspects of the Cyclopropene to Vinylcarbene Rear
rangement 117
*
M. Christl ,M. Braun
Generation and Interception of 1-0xa-2,3-cyclohexadiene and 1,2,4-Cyclohexa
triene 121
K.J. Shea
On the Relationship Between Strain and Chemical Reactivity of Torsionally
Distorted Carbon-Carbon Double Bonds 133
P. G. Gassman
Photoinduced Single Electron Transfer from Strained Rings 143
viii
S. Nishida
Chemical Behaviour of Cation Radicals Derived from Strained Molecules in
Solution. Spiro-Activation in the Cleavage of Some Arylcyclopropanes upon
Treatment with TCNE or DDQ 169
C.J.Suckling
The Cyclopropyl Group in Studies of Enzyme-Catalysed Reactions 177
*
B. Ernst ,A. de Mesmaeker, H. Greuter, S. J. Veenstra
Intramolecular [2+2)-Cycloadditions of Ketenes and Olefins 207
*
L. Ghosez ,C. Lian Yong, B. Gobeaux, C. Houge, I. Marko, M. Perry,
H. Saimoto
Strained Iminium Salts in Synthesis 235
*
R. D. Miller , W. Theis, G. Heilig, S. Kirchmeyer
The Generation and Rearrangement of 2-Diazocarbonyl Cyclobutanones: The
Formation of 5-Spirocyclopropyl-2(5H)furanones 255
*
E. Osawa ,J. M. Rudzinski, D. A. Barbiric, E. D. Jemmis
Computational Studies of Prismane. Helvetane/lsraelane and Asterane 259
*
Z. Goldschmidt , H. E. Gottlieb
Cyclobutane-Cyclopentane Interconversion of Coordinated Adducts of Cyclohepta
triene and Tetracyanoethylene via the [2.2J-Sigmahaptotropic Rearrangement 263
G. Mehta
Quest for Higher Prismanes 269
*
R. Keese , W. Luef, L. Mani, S. Schuttel
Planarizing Distortions in Polycyclic Carbon Compounds 283
*
H. Hopf ,C. Marquard
Strain Release in Aromatic Molecules: The [2n)-Cyclophanes 297
*
A. Krief ,P. Surleraux, W. Dumont, P. Pasau, Ph. Lecomte, Ph. Barberaux
Trip around the Three-Membered Cycles Syntheses 333
*
K. B. Wiberg ,D. R. Artis
Experimental and Theoretical Studies of Bridged Cyclopropenes 349
G. Szeimies
From Bicyclo[1.1.0)butanes to [n.1.1)Propelianes 361
z.
Yoshida
New Aspects of Highly Strained Ring Chemistry 383
*
B. Zwanenburg ,A. J. H. Klunder
Strained Cage Systems: SynthetiC and Structural Implications 405
ix
*
L. Fitjer ,A. Kanschik, M. Majewski
Studies on the Synthesis of Cyclopentanoic Sesquiterpenes via Rearrangement
Routes: WModhephene and Wlsocumene 431
C. J. M. Stirling
Directionality in Formation of Small Rings by Intramolecular Nucleophilic Substi
tution 439
*
C. Almansa, M. L. Garcia, C. Jaime, A. Moyano, M. A. Pericas, F. Serratosa
Synthesis, Chiroptical Properties and Synthetic Applications of Perhydrotriquina
cene-1 .4,7 -trione 447
w.
E. Billups
Reactions of Strained Carbon-Carbon Bonds with Metal Atoms 451
*
Y. Apeloig ,M. Karni, D. Arad
Cyclopropabenzenes and Alkylidenecyclopropabenzenes. A Synergistic Relation
between Theory and Experiment 457
*
J. Michl, P. Kaszynski, A. C. Friedli, G. S. Murthy, H.-C. Yang, R. E. Robinson,
N. D. McMurdie, T. Kim
Harnessing Strain: From [1.1.1 ]propellanes to Tinkertoys 463
*
W. E. Billups ,M. M. Haley, G.-A. Lee
Synthesis of Cyclopropenes 483
*
R. Boese ,D. Blaser
How to Get Structures of Strained Compounds: Low Temperature Structures and
X-X Electron Deformation Densities 485
*
S. Braverman , Y. Duar
Novel Intramolecular l,l-Cycloadditions of Diazoallenes 489
*
A. Fadel, B. Karkour, J. Ollivier, J. Salaun
Efficient Route to Optically Active Strained Compounds 493
*
W. Grimme ,W. Neukam
Anionic (3 + 2)-Cycloreversion of Strained Cage Nitriles 495
* .
A. Krebs ,A. Jacobsen-Bauer, E. Haupt, M. Veith, V. Huch
Reaction of an Angle Strained Cycloheptyne with a Stabilized Stannylene
Synthesis and X-Ray Structure of a Distannacyclobutene System 497
*
O. M. Nefedov ,S. P. Kolesnikov, M. P. Egorov, A. Krebs, Yu. T. Struchkov
Structure and Reactivity of Small Heterocycles Containing Germanium Atoms 499
*
H. Bothe, A.-D. SchlUter
Relief of Strain Energy as Driving Force in Ring-Opening Polymerizations of a
[l.1.1]Propellane 503
x
*
T. Thiemann, S. Kohlstruk, G. Schwer, A. de Meijere
Dials-Alder Reactions of Siloxyallylidenecyclopropanes: Facile Syntheses of Spiro-
[2.5]octan-3-ones 507
*
N. Krass, L. Wessjohann, D. Yu, A. de Meijere
Cyclopropyl Group Containing Amino Acids from a-Chlorocyclopropylidenacetates 509
*
S. Wyn Roberts, C. J. M. Stirling
Eliminative Fission of Strained Cycloalkoxides - The Question of Electrophilic 513
Catalysis
*
P. A. Krackman, W. H. de Wolf , F. Bickelhaupt
Special Reactivity of 8,11-Dihalo[5]metacyclophane 515
*
G. B. M. Kostermans, W. H. de Wolf , F. Bickelhaupt
Small [n] Cyclophanes. Where is the Limit? 517
Index 519
FORMAT OF THE CONFERENCE
AND CORRESPONDING CONTRIBUTIONS TO THIS VOLUME
Invited lectures
B. M. Trost 1
K. N. Houk 25
E. Piers 39
H. U. Reissig *, R. Zschiesche, A. Wienand, M. Buchert 51
W. Ando *, N. Tokitoh 59
L A. Paquette *, J. Dressel 77
P. G. Gassman 143
S. Nishida 169
C. J. Suckling 177
B. Ernst*, A. de Mesmaeker, H. Greuter, S. J. Veenstra 207
L Ghosez*, C. Lian Yong, B. Gobeaux, C. Houge, I. Marko, M. Perry, H. Saimoto 235
G. Mehta 269
R. Keese *, W. Luef, L Mani, S. Schuttel 283
H. Hopt*, C. Marquard 297
A. Kriet*, P. Surleraux, W. Dumont, P. Pasau, Ph. Lecomte, Ph. Barberaux 333
K. B. Wiberg *, D. R. Artis 349
G. Szeimies 361
Z. Yoshida 383
B. Zwanenburg *, A. J. H. Klunder 405
J. Michl*, P. Kaszynski, A. C. Friedli, G. S. Murthy, H.-C. Yang, R. E. Robinson,
N. D. McMurdie, T. Kim 463
Contributed papers
T. Hudlicky* , A. Fleming, T. Lovelace, G. Seoane, K. Gadamasetti, G. Sinai-Zingde 109
M. S. Baird*, J. R. AI-Dulayymi, H. H. Hussain 117
M. Christl*, M. Braun 121
K. J. Shea 133
R. D. Miller *, W. Theis, G. Heilig, S. Kirchmeyer 255
E. Osawa *, J. M. Rudzinski, D. A. Barbiric, E. D. Jemmis 259
Z. Goldschmidt* , H. E. Gottlieb 263
L Fitjer *, A. Kanschik, M. Majewski 431
C. J. M. Stirling 439
C. Almansa, M. L Garcia, C. Jaime, A. Moyano, M. A. Pericas, F. Serratosa * 447
W. E. Billulls 451
Y. Apeloig , M. Karni, D. Arad 457
Posters
W. E. Billups *, M. M. Haley, G.-A. Lee 483
R. Boese*, D. Blaser 485
S. Braverman*, Y. Duar 489
A. Fadel, B. Karkour, J. Ollivier, J. Salaun * 493
W. Grimme *, W. Neukam 495
A. Krebs *, A. Jacobsen-Bauer, E. Haupt, M. Veith, V. Huch 497
O. M. Nefedov*, S. P. Kolesnikov, M. P. Egorov, A. Krebs, Yu. T. Struchkov 499
H. Bothe, A.-D. SchlUter* 503
T. Thiemann, S. Kohlstruk, G. Schwar, A. de Meijere * 507
xi