Table Of ContentTopics in Current Chemistry
Editorial Board:
A. de Meijere K.N. Houk H. Kessler
J.-M. Lehn S.V. Ley S.L. Schreiber J. Thiem
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B. M. Trost F. Vogtle H. Yamamoto
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Stereoselective Heterocyclic
Synthesis Ill
Volume Editor: Peter Metz
With contributions by
A. Hassner, I. N. N. Namboothiri,
U. Nubbemeyer, S. D. Rychnovsky, C. J. Sinz,
P. ten Holte, B. Zwanenburg
Springer
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Volume Editor
Prof. Dr. Peter Metz
Institut fiir Organische Chemie
Technische Universitat Dresden
Mommsenstraf3e 13
01062 Dresden, Germany
E-mail:m [email protected]
Editorial Board
Prof. Dr. Armin de Meijere Prof. K.N. Houk
lnstitut fur Organische Chemie Department of Chemistry and Biochemistry
der Georg-August-Universitat University of California
Tammannstrde 2 405 Hilgard Avenue
37077 GGttingen, Germany Los Angeles, CA 90024-1589, USA
E-mail: amever1 @uni-goettingen.de E-mail: [email protected]
Prof. Dr. Horst Kessler Prof. Jean-Marie Lehn
Institut fiir Organische Chemie Institut de Chimie
TC Munchen UniversitC de Strasbourg
Lichtenbergstrde 4 1 rue Blaise Pascal, B. P.Z 296lR8
85747 Garching, Germany 67008 Strasbourg Cedex, France
E-mail: [email protected] E-mail: [email protected]
Prof. Steven V. Ley Prof. Stuart L. Schreiber
University Chemical Laboratory Chemical Laboratories
Lensfield Road Harvard University
Cambridge CB2 lEW, Great Britain 12 Oxford Street
E-mail: [email protected] Cambridge, MA 021 38-2902, USA
E-mail: [email protected]
Prof. Dr. Joachim Thiem
Prof. Barry M. Trost
Institut fur Organische Chemie
bur^
Universitit Department of Chemistry
Martin-Luther-King-Platz 6 Stanford University
20146 Hamburg, Germany Stanford, CA 94305-5080, USA
E-mail: [email protected] E-mail: [email protected]
Prof. Dr. Fritz Vogtle Prof. Hisashi Yamamoto
Kekule-Institutf iir Organische Chemie School of Engineering
und Biochemie der Universitat Bonn Xagoya Cniversity
Gerhard-Domagk-Strai3e 1 Chikusa, Nagoya 464-01, Japan
53121 Bonn, Germany E-mail: [email protected]
E-mail: voegtMuni-burtn.de
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Preface
Keeping up with the advances in modern heterocyclic chemistry is essential for
many of our colleagues in academia and industry. It is the aim of this series on
"Stereoselective Heterocyclic Synthesis" to assist the chemical community in
this respect by presenting a selection of exciting recent developments. As it was
for the first two volumes (1997), the stereoselective synthesis of - or with the aid
of - heterocycles is the common motif for all the chapters in this third volume.
I am very glad that again leading researchers in this area have contribut-
ed highly stimulating accounts with up-to-date coverage. "Stereoselective
Heterocyclic Synthesis 111" features chapters on "Stereoselective Intramolecular
J,3-Dipolar Cycloadditions" by I.N.N. Nambothiiri and A. Hassner giving an
in depth survey of the generation and synthetic application of valuable
1,3-dipoles,"4-Acetoxy- and 4-Cyano-12-dioxanes in Synthesis" by C. J. Sinz and
S.D. Rychnovsky presenting a comprehensive summary of the utility of the
versatile title compounds in natural products synthesis,"The Synthetic Potential
of Three-Membered Ring Aza-Heterocycles" by B. Zwanenburg and l? ten Holte
highlighting the fascinating chemistry of aziridine and azirine carboxylic esters,
and '(Synthesis of Medium-Sized Ring Lactams" by U. Nubbemeyer discussing a
wide range of modern strategies for the stereoselective preparation of these
important heterocycles.
I wish to express my thanks to all contributors for their dedicated effort and
to Mrs. Kollmar-Thoni, Springer-Verlag, for her continuous support.
Dresden, March 2001 Peter Metz
Contents
Stereoselective Intramolecular 1.3 .Dipolar Cycloadditions
I.N.N. Namboothiri. A . Hassner . . . . . . . . . . . . . . . . . . . . . . . 1
4Acetoxy- and 4-Cyano-1J-dioxanes in Synthesis
. . . . . . . . . . . . . . . . . . . . . . . . . .
C.J.Sinz.S.D.Rychnovsky 51
The Synthetic Potential of Three-Membered Ring Aza-Heterocycles
. . . . . . . . . . . . . . . . . . . . . . . . . . .
B Zwanenburg. P ten Holte 93
Synthesis of Medium-Sized Ring Lactams
U. Nubbemeyer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Author IndexVolumes 201 .21 6 . . . . . . . . . . . . . . . . . . . . . . . 197
Contents of Volume 189
Stereoselective Heterocyclic Synthesis I
Volume Editors: P. Metz
ISBN 3-540-62678-6
Hetero Diels-AIder Reactions in Organic Chemistry
L.F. Tietze, G. Kettschau
Tandem Processes of Metallo Carbenoids for the Synthesis of Azapolycycles
A. Pawda
Contents of Volume 190
Stereoselective Heterocyclic Synthesis I I
Volume Editors: P. Metz
ISBN 3-540-62700-6
Using Ring-Opening Reactions of Oxabicyclic Compounds as a Strategy
in Organic Synthesis
P. Chiu, M. Lautens
The Nucleophilic AdditionlRing Closure (NARC) Sequence
for the Stereocontrolled Synthesis of Heterocycles
P. Perlmutter
Chiral Acetylenic Sulfoxides and Related Compounds in Organic Synthesis
A.W.M. Lee, W.H. Chan
N-Sulfonyl Imines - Useful Synthons in Stereoselective Organic Synthesis
S. M. Weinreb
Stereoselective Intramolecular
1,3-Dipolar Cycloadditions
Irishi N.N.Namboothiri1· Alfred Hassner2
1 Department ofChemistry,Indian Institute ofTechnology,Bombay,Mumbai 400 076,India
E-mail:[email protected]
2 Department ofChemistry,Bar-Ilan University,Ramat Gan 52900,Israel
E-mail:[email protected]
An in depth account ofintramolecular 1,3-dipolar cycloadditions involving dipoles such as
nitrile oxides,silyl nitronates,H-nitrones,azides,and nitrilimines is presented with particu-
lar emphasis on the stereochemistry during the cycloaddition.Various methods employed for
the generation ofthe dipoles and their applications to stereoselective synthesis are also dis-
cussed.
Keywords: Intramolecular 1,3-dipolar cycloadditions, Stereoselectivity, Nitrile oxides, Silyl
nitronates,Oximes,H-Nitrones,Azides,Nitrilimines
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Intramolecular Nitrile Oxide Cycloaddition (INOC) . . . . . . . . . 2
2.1 Some General Factors Influencing the Cycloaddition . . . . . . . . . 3
2.2 Nitrile Oxides from Oximes . . . . . . . . . . . . . . . . . . . . . . . 4
2.2.1 a-Bromoaldoximes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.3 Nitrile Oxides from Nitro Alkanes . . . . . . . . . . . . . . . . . . . 13
3 Intramolecular Silyl Nitronate-Olefin Cycloaddition (ISOC) . . . . 21
3.1 INOC vs ISOC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.2 One-Pot Reactions Involving Michael Addition and ISOC . . . . . . 23
3.3 Sequential 1,3-Dipolar Cycloadditions . . . . . . . . . . . . . . . . . 27
3.4 Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4 Intramolecular Oxime-Olefin Cycloaddition (IOOC) . . . . . . . . . 30
4.1 (H)-Nitrones from Oximes . . . . . . . . . . . . . . . . . . . . . . . . 30
4.1.1 Pyrrolidines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
4.1.2 Carbocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4.1.3 Fused Rings (Pyrrolizidines,Indolizidines,and Quinolizidines) . . . 35
4.1.4 Tetrahydrofurans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
4.2 Role ofSubstituents in the Oxime-(H)-Nitrone Isomerization . . . . 36
4.3 Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
5 Intramolecular Azide-Olefin Cycloaddition (IAOC) . . . . . . . . . 39
5.1 Azides to Triazolines,Imines,and Aziridines . . . . . . . . . . . . . 39
5.2 a-Azido Ethers to D3-Oxazolines . . . . . . . . . . . . . . . . . . . . 40
5.3 IAOC in the Synthesis ofBioactive Materials . . . . . . . . . . . . . 42
Topics in Current Chemistry,Vol.216
© Springer-Verlag Berlin Heidelberg 2001
