Organic Chemistry in Action: The Design of Organic Synthesis

567 Pages·1996·17.15 MB·English

by  Fèlix Serratosa (Eds.)

Studies in Organic Chemistry 51
ORGANIC CHEMISTRY
IN ACTION
The Design of Organic Synthesis
SECOND EDITION
This Page Intentionally Left Blank
Studies in Organic Chemistry 51
O R G A N I C
C H E M I S T R Y
I N A C T I O N
The Design of Organic
Synthesis
SECOND EDITION
PART A:
F~lix Serratosat
Formerly at the Department of Organic Chemistry, University of
Barcelona, 08028-Barcelona, Spain
PART B:
Josep Xicart
Laboratory of Organic Chemistry, Faculty of Pharmacy, University of
Barcelona, 08028-Barcelona, Spain
and
F~lix Serratosat
Formerly at the Department of Organic Chemistry, University of
Barcelona, 08028-Barcelona, Spain
with a copy of CHAOS and CHAOSBASE
1996
ELSEVIER
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Studies in Organic Chemistry
Titles in this series:
1 Complex Hydrides by A. Haj6s
2 Proteoglycans-Biological and Chemical Aspects in Human Life
by J.F. Kennedy
3 New Trends in Heterocyclic Chemistry edited by R.B. Mitra, N.R. Ayyangar,
V.N. Gogte, R.M. Acheson and N. Cromwell
4 Inositol Phosphates: Their Chemistry, Biochemistry and Physiology
by D.J. Gosgrove
5 Comprehensive Carbanion Chemistry. Part A. Structure and Reactivity edited by
E. Buncel and T. Durst
Comprehensive Carbanion Chemistry. Part B. Selectivity in Carbon-Carbon
Bond Forming Reactions edited by E. Buncel and T. Durst
6 New Synthetic Methodology and Biologically Active Substances edited
by Z.-I. Yoshida
7 Quinonediazides by V.V. Ershov, G.A. Nikiforov and C.R.H.I. de Jonge
8 Synthesis of Acetylenes, Allenes and Cumulenes: A Laboratory Manual
by L. Brandsma and H.D. Verkruijsse
9 Electrophilic Additions to Unsaturated Systems by P.B.D. de la Mare and
R. Bolton
10 Chemical Approaches to Understanding Enzyme Catalysis: Biomimetic
Chemistry and Transition-State Analogs edited by B.S. Green, Y. Ashani and
D.Chipman
11 Flavonoids and Bioflavonoids 1981 edited by L. Farkas, M. Gfibor, F. Kfillay and
H.Wagner
12 Crown Compounds: Their Characteristics and Applications by M. Hiraoka
13 Biomimetic Chemistry edited by Z.-I. Yoshida and N. Ise
14 Electron Deficient Aromatic- and Heteroaromatic-Base Interactions.
The Chemistry and Anionic Sigma Complexes by E. Buncel, M.R. Crampton,
M.J. Strauss and F. Terrier
15 Ozone and its Reactions with Organic Compounds by S.D. Razumovskii and
G.E. Zaikov
16 Non-benzenoid Conjugated Carbocyclic Compounds by D. Lloyd
17 Chemistry and Biotechnology of Biologically Active Natural Products edited by Cs.
Sz~ntay, A Gottsegen and G. Kov~cs
18 Bio-Organic Heterocycles: Synthetic, Physical, Organic and Pharmacological
Aspects edited by H.C. van der Plas, L. (~tvt~s and M. Simonyi
19 Organic Sulfur Chemistry: Theoretical and Experimental Advances edited by
F. Bernardi, I.G. Csizmadia and A. Mangini
20 Natural Products Chemistry 1984 edited by R.I. Zalewski and J.J. Skolik
21 Carbocation Chemistry by P. Vogel
22 Biocatalysis in Organic Syntheses edited by J. Tramper, H.C. van der Plas and
P. Linko
23 Flavonoids and Bioflavonoids 1985 edited by L. Farkas, M. G~bor and F. K~llay
24 The Organic Chemistry of Nucleic Acids by Y. Mizuno
25 New Synthetic Methodology and Functionally Interesting Compounds edited by
Z. -I. Yoshida
26 New Trends in Natural Products Chemistry 1986 edited by Atta-ur-Rahman and
P.W. Le Quesne
27 Bio-Organic Heterocycles 1986. Synthesis, Mechanisms and Bioactivity edited by
H.C. van der Plas, M. Simonyi, F.C. Alderweireldt and J.A. Lepoivre
28 Perspectives in the Organic Chemistry of Sulfur edited by B. Zwanenburg and
A.H.J. Klunder
29 Biocatalysis in Organic Media edited by C. Laane, J. Tramper and M.D. Lilly
30 Recent Advances in Electroorganic Synthesis edited by S. Torii
31 Physical Organic Chemistry 1986 edited by M. Kobayashi
32 Organic Solid State Chemistry edited by G.R. Desiraju
33 The Role of Oxygen in Chemistry and Biochemistry edited by W. Ando and
Y. Moro-oka
34 Preparative Acetylenic Chemistry, second edition by L. Brandsma
35 Chemistry of Hetrocyclic Compounds edited by J. Kov~ic and P. Z~ilupsk~
36 Polysaccharides. Syntheses, Modifications and Structure/Property Relations by
M. Yalpani
37 Organic High Pressure Chemistry by W.J. Le Noble
38 Chemistry of Alicyclic Compounds. Structure and Chemical Transformations by
G. Haufe and G. Mann
39 Carbon-13 NMR of Flavonoids edited by P.K. Agrawal
40 Photochromism. Molecules and Systems edited by H. Dtirr and H. Bouas-Laurent
41 Organic Chemistry in Action. The Design of Organic Synthesis by F. Serratosa
42 Similarity Models in Organic Chemistry, Biochemistry and Related Fields edited by
J. Shorter, R.I. Zalewski and T.M. Krygowski
43 Piperidine. Structure, Preparation, Reactivity, and Synthetic Applications of
Piperidine and its Derivatives by M. Rubiralta, E. Giralt and A. Diez
44 Cyclobutarenes. The Chemistry of Benzocyclobutene, Biphenylene, and Related
Compounds by M.K. Shepherd
45 Crown Ethers and Analogous Compounds edited by M. Hiraoka
46 Biocatalysts in Organic Synthesis by J. Halga~
47 Stability and Stabilization of Enzymes edited by W.J.J. van den Tweel, A. Harder and
R.M. Buitelaar
48 Organofluorine Compounds in Medicinal Chemistry and Biomedical Applications
edited by R. Filler, Y. Kobayashi and L.M. Yagupolskii
49 Catalyzed Direct Reactions of Silicon edited by K.M. Lewis and D.G. Rethwisch
50 Organic Reactions-Equilibria, Kinetics and Mechanism by F. Ruff
and I.G. Csizmadia
51 Organic Chemistry in Action. The Design of Organic Synthesis (Second Edition)
by F. Serratosa and J. Xicart
VII
PREFACE TO THE FIRST EDITION
In 1975, under the title "HEURISKO. Introducci6n a la Sfntesis Org~inica",
I published a book which had been written mostly in thhe academic year 1970-71
and copies of which circulated at that time among the graduate students of the
Organic Chemistry Department (University of Barcelona). Although in the year
1969 Professor R.E. IRELAND had published his book "Organic Synthesis"
(Prentice-Hall), which had a rather classical approach, it was evident that starting
from 1967, Professor E.J.COREY, with his methodology and formalisation of the
synthetic process, had made a fundamental contribution to the systematisation of
organic synthesis which was, from a didactic point of view, a breakthrough in the
way Organic Synthesis was taught. Since in my incipient book some of COREY's
ideas were already collected, the time seemed ripe for an updating and to look for a
publisher. Finally, Editorial Alhambra (Madrid) included it in the collection
EXEDRA, a series of monographs on natural and physical sciences. One year later,
in 1976, the book by Dr. S. TURNER "The Design of Organic Syntheses"
(Elsevier, Amsterdam) was published, thus confirming the expediency of my
decision. Later on, S. WARREN published two textbooks: in 1978 a short but
really useful book for undergraduates entitled "Designing Organic Syntheses. A
Programmed Introduction to the Synthon Approach", and then, in 1982, a larger
book "Organic Synthesis: The Disconnection Approach" (both from John Wiley &
Sons, Chichester). In 1983, J. FUHRHOP and G. PENZLIN published their book
"Organic Synthesis" (Verlag Chemie, Weinheim) and finally, very recently, in the
middle of 1989, the book by E.J. COREY and X.M. CHENG "The Logic of
Chemical Synthesis" (John Wiley & Sons, New York) appeared.
In the meantime, in 1985, when I started to prepare a second edition of
"HEURISKO" I realised that my teaching experience in the last fifteen years had
changed my own perspective of the topic sufficiently so as to offer a book
essentially different, in which the principles, the strategies and the methodologies
for designing organic syntheses could be presented in a simple and yet rigorous
way to advanced undergraduate students (corresponding to the fifth year in Spanish
Universities). The decision to publish this new book in English was taken later,
when Elsevier Science Publishers became interested in the project.
VIII
If in the preface of my first book I was pleased to acknowledge my gratitude
to Professor E.J. COREY; now, as stated below in the "Acknowledgements", I
wish to extend my gratitude to Professor D.A. EVANS.
The treatment given in this book is orientative rather than exhaustive, with
special emphasis on the "Lapworth-Evans model" of alternating polarities and the
"heuristic principles" governing the different strategies and methodologies involved
in the design of organic syntheses. The program, which runs on an IBM PC or a
fully compatible microcomputer, allows the "heuristic method" to be used. That is
to say, the pupils may be trained to learn and find results by themselves.
This book does not pretend to replace or invalidate any other book on the
field. It is one more book in the field of organic synthesis in which teachers and/or
students may perhaps find some stimulating ideas and some new examples to deal
with.
The title of the book was just a compromise with the Publishers. Because
most of the aspects are treated in the book in a rather fragmentary manner and they
reflect my own interests which I have freely expressed (sometimes with immoderate
enthusiasm and spontaneity) in the classrooms for almost three decades, an
appropiate titled could be "Lectures on Organic Synthesis", to which the subtitle
"An Introduction to Corey's and Lapworth-Evans Methodologies" might be added.
Nevertheless, no matter how fragmentary the different topics may be, I have tried to
ensure that the ideas flow smoothly, from a basic introduction to organic synthesis
to the methodology of organic synthesis using modern terminology, based on
EVANS' work. I hope my efforts will not be in vain and the book will receive an
"acceptable" acceptance.
Sitges, New Year's Day, 1990
F6lix Serratosa
Research Professor, C.S.I.C.
IX
FOREWORD TO THE SECOND EDITION
The cordial reception which the first edition of the book received from
teachers and students has prompted us to take the opportunity offered by the
publishers to prepare a new revised edition.
Some new material has been added, the more significant changes being:
1) The book has been restructured in two well differentiated parts. Part B
deals exclusively with computer-assisted organic synthesis (see 8 and 9).
2) Emphasis on the new objectives and targets, as well as on the role that
organic synthesis should play from now on in the new areas of supramolecular
chemistry and bioorganic chemistry (Chapter 1), is made.
3) A more extended discussion on synthetic methods and strategies based
in radical carbon-carbon bond-forming reactions has been included (Chapter 7).
4) Some new examples to illustrate the heuristic principles have been
incorporated (Chapter 4, for instance)
5) The chapter on alicyclic stereoselection has been splitted in two
chapters (9 and 10). Chapter 10, which is exclusively devoted to Sharpless'
asymmetric epoxidation and dihydroxylation, has been rewritten de novo. The most
recent advances in catalytic and stereoselective aldol reactions are incorporated in
Chapter 9.
6) Chapter 11 is a new one and the aim of it is, on the one hand, to
present a panoramic view of the most important methods for the preparation of
optically pure compounds in industrial scale (chirotechnology) and, on the other, to
give a brief inside into the new biological synthetic methodologies, such as the use
of enzymes and catalytic monoclonal antibodies or abzymes, which are becoming
more and more important and familiar to the synthetic organic chemist. As stated by
G. H. Whitesides and C. H. Wong (Angew. Chem., Int. Ed. Engl. 1985, 24,
617-638): "Those unwilling to use these and other biological derived synthetic
techniques may find themselves exluded from some of the most exciting problems
in molecular science".
7) The chapter dealing with examples of retrosynthetic analysis and the
corresponding total synthesis has been enlarged and includes new syntheses of
natural products (Chapter 13).