Electrochemistry VI Electroorganic Synthesis: Bond Formation at Anode and Cathode

191 Pages·1997·3.107 MB·English

by  R. Daniel Little, Michael K. Schwaebe (auth.), Prof. E. Steckhan (eds.)

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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
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ISSN 0340-1022
ISBN 3-540-61454-0 Springer-Verlag Berlin Heidelberg NewYork
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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:
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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