Table Of Content8 5 scipoT ni tnerruC yrtsimehC
regnirpS
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Electrochemistry VI
Electroorganic Synthesis:
Bond Formation ta Anode
and Cathode
emuloV :rotidE n.aEhkcetS
With snoitubirtnoc by
R. D. Little, K. D. Moeller, J.-Y. N6d61ec,
J. P6richon, M. K. Schwaebe, I. Tabakovic,
M. Troupel
2 With Figures dna 34 Tables
~ regnirpS
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.
As a rule, contributions are specially commissioned. The editors and publishers will,
however, always be pleased to receive suggestions and supplementary information.
Reviews are accepted for "Topics in Current Chemistry" in English.
In references Topics in Current Chemistry is abbreviated Top.Curr.Chem. and is
cited as a journal.
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ISSN 0340-1022
ISBN 3-540-61454-0 Springer-Verlag Berlin Heidelberg NewYork
Library of Congress Catalog Card Number 74-644622
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Volume Editor
Prof. E. Steckhan
Rheinische Friedrich-Wilhelms-Universitat Bonn
Institut Organische filr Chemie und Biochemie
Gerhard-Domagk-Stral3e 1
D-53121 Bonn, FRG
Editorial Board
.forP .rD Armin de Meijere Institut for Organische Chemie der ,ti~tisrevinU-tsuguA-groeG
eBartsnnammaT 2, G6ttingen, 37077 FRG
e-mail: [email protected]
.forP .rD K. N. Houk University of California, Department
of Chemistry and Biochemistry, 504 Hilgard Avenue,
Los Angeles, AC ,9851-42009 USA
e-mail: [email protected]
.forP .rD Jean-Marie Lehn Institut ed Chimie, Universit6 ed Strasbourg,
rue Blaise 1 Pascal, .B .P Z 296/R8, F-67008 Cedex, Strasbourg
France
e-mail: [email protected]
.forP Steven E Ley University Chemical Laboratory, Lensfield Road,
2BC WE1 Cambridge, England
e-mail: [email protected]
.forP .rD Joachim Thiem Institut fur Organisehe Chemie, Universitat Hamburg,
Martin-Luther-King-Platz ,6 Hamburg, 20146 FRG
e-mail:[email protected]
.forP Barry M. Trost Department of Chemistry, University, Stanford
Stanford, AC ,0805-50349 USA
e-mail: [email protected]
.forP .rD Fritz eltg~iV Institut fur Organische Bioehemie und Chemie der ,ti~tisrevinU
eBartS-kgamoD-drahreG ,1 12135 Bonn, FRG
e-mail: [email protected]
.forP Hisashi Yamamoto School of Engineering, Nagoya University,
10-464 Chikusa, Nagoya, Japan
[email protected] e-mail:
Editorial Statement
The series Topics in Current Chemistry was founded in 1949 as "Fortschritte der
chemischen Forschung" (meaning "advances in chemical research"). The aims and
scope at thatt ime read as follows (translation from the German).
"The purpose [of the series] is to report on advances in areas of the chemical
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of all published results, but rather the critical examination of the literature and the
elucidation of the main directions that developments are taking. Likewise, these
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chemists, who want to inform themselves about areas bordering ont heir work."
This concepta nd the publication of topical volumes from the beginning showed
an amazing foresight on the part of the founding editors. Over the years progress in
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per year has increased tremendously. At the same time the application of the powerful
tools of chemical investigation to other fields has led to a growing understanding of
the chemical basis of the natural, medical and material sciences, with the result that
the chemical sciences have become increasingly interdisciplinary. Through all these
changes the original concept and organization of Topics in Current Chemistry has
allowed it to continue to play an important role in the secondary literature. Indeed,
with the rapidly changing landscape of the chemical sciences, the need for such a
series is ever increasing.
As we look to the future, the challenges and opportunities facing the chemical
research community areg reat. It is the goal of the current editorial boartdo continue
to provide that community with topical volumes containing critical reviews of the
present and future trends across the entire range of the modem chemical sciences.
We join Springer-Verlag in thanking the editors now leaving the editorial board,
Jack D. Dunitz, Klaus Hafner, Sho Ito, Kenneth N. Raymond and Charles W. Rees,
whose efforts over the last decades served to maintain the high standards of this
series.
Armin de Meijere, G6ttingen Joachim Thiem, Hamburg
Kendall N. Houk, Los Angeles Barry M. Trost, Stanford
Jean-Marie Lehn, Strasbourg Fritz VOgtle, Bonn
Steven V. Ley, Cambridge, UK Hisashi Yamamoto, Nagoya
Preface
In organic chemistry the strategic steps in complex syntheses are bond forming
reactions. Therefore, as mature method, electroorganic has to compete with the
powerful repertoire of alternative synthetic processes which have been developed
for this pupose in recent years. The volume Electrochemistry VI of Topics Current in
Chemistry reviews the state of the art of modern bond forming reactions at the anode
and cathode, demonstrating that they continue to be highly competitive with alterna-
tive methods. It highlights both the current value and the large potential of organic
electrochemistry thef or selective formation of carbon-carbon and carbon-heteroatom
bonds and for the generation of complex organic molecules using electrochemical
key steps. The utility of electrochemistry for the generation of highly reactive
intermediates under mild conditions and for the selective reversal of the polarity of
functional groups is demonstrated for ring forming reactions and carbon-carbon
cross-coupling reactions. The contents range fromt he synthesis of natural products
ttoh e preparation of pharmaceuticals, from the generation of unsymmetrical biaryls
to the construction ofpeptide mimetics. electrochemical The prodedures critically are
compared with alternative chemical processes and mechanistic considerations are
included. As guest editor I am very thankful that again well known experts in their
fields agreed to contribute four concise reviews to this volume.
Bonn, October 1996 Prof. Steckhan
Table of Contents
Reductive Cyclizations at the Cathode
R. D. Little and M. K. Schwaebe ......................
Intramolecular Carbon - Carbon Bond
Forming Reactions at the Anode
K. D. Moeller ..................................... 49
Anodic Synthesis of Heterocyclic Compounds
I. Tabakovic ...................................... 87
Organic Electroreductive Coupling Reactions
Using Transition Metal Complexes as Catalysts
J.-Y. N6d61ec, J. P6richon and M. Troupel ............... 141
Author Index Volumes 151-185 ..................... 175
Table of Contents of Volume 170
Electrochemistry V
Electrochemical Reactions of Fluoro Organic Compounds
T. Fuchigami
Electrochemical Reactions of Organosilicon Compounds
J. Yoshida
Electroenzymatic Synthesis
E. Steckhan
Electrochemistry for a Better Environment
P. M. Bersier, L. Carlsson and J. Bersier
Reductive Cyclizations at the Cathode
R. Daniel Little and Michael K. Schwaebe
Department of Chemistry, University of California, Santa Barbara, CA 93106,
USA
Table of Contents
1 Introduction .......................................... 2
2 Electrohydrocyclization ................................. 3
2.1 An Application to Natural Products Synthesis: Sterpurene... 4
2.2 Allene Tethered to ~,/~-Unsaturated Ester ................ 6
2.3 Variations on a Theme: Bis-Imine Cyclization ............ 7
3 Variations on a Theme .................................. 8
3.1 Electroreductive Cyclization: Electron Deficient
Alkene/Carbonyl ................................... 8
3.1.1 Mechanism .................................. 9
3.1.2 An Approach to Pentalenolactone E Methyl Ester ..... 11
3.1.3 Formal Total Synthesis of Quadrone .............. 13
3.1.4 The [3.2.1] Framework: Scope and Limitations ...... 15
3.2 Non-Conjugated Alkene/Carbonyl ..................... 81
3.3 Alkene/Ester ...................................... 21
3.4 Allene and Alkyne Acceptors/Carbonyl ................. 21
3.5 Nitrile/Carbonyl ................................... 22
3.6 The Aromatic/Carbonyl Variation ..................... 26
3.7 Pyridinium/Carbonyl ............................... 29
4 Tandem Cyclizations ................................... 31
4.1 Tandem Cyclization of Non-Conjugated Dienones ......... 31
4.2 Enol Phosphates of 1,3-Dicarbonyl Compounds .......... 32
4.3 Tandem Cyclization of Enol Phosphates ................ 34
Topics in Current Chemistry, Vok 581
© Springer-Verlag Berlin Heidelberg 1997
