Modern Synthetic Methods 1989

310 Pages·1989·6.374 MB·English

by  Prof. Dr. Rolf Scheffold (auth.)

MODERN SYNTHETIC METHODS
Volume 5 . 1989
Editor:
Prof Dr. Rolf Scheffo ld
Institut fUr organische Chemie
der Universitiit Bern
FreiestraBe 3
CH-3012 Bern
MODERN SYNTHETIC METHODS
Editor: R. Scheffo ld
Volume 1 . 1976
M. Makosza, Naked Anions - Phase Transfer
A. Patchornik, Polymer Supported Reagents
D. Seebach, S-and Se-Reagents
1976 Verlag Sauerliinder, Otto Salle, Aarau und Frankfurt am Main
Volume 2 . 1980
L. Eberson, Electro-Organic Synthesis
Chiral Building Blocks in Enantiomer Synthesis:
D. Seebach - ex Tartaric Acid
A. Vasella - ex Sugars
A. Fischli - Using Enzymatic Transformations
1980 Verlag Sauerliinder, Otto Salle, Aarau und Frankfurt am Main
Volume 3 . 1983
Transition Metals in Organic Synthesis:
J. K. Stille, Principles and Rules
L. S. Hegedus, Group VIII Transition Metals
J. F. Normant, Copper and Manganese
D. Seebach, Titanium and Zirconium
R. Scheffo ld, Bl2 and Related Cobalt Complexes
1983 Verlag Sauerliinder, Otto Salle, Aarau und Frankfurt am Main
Coedition by John Wiley & Sons, Inc., Chichester
Volume 4 . 1986
Sound and Light in Synthesis:
K. S. Suslick, Ultrasound in Synthesis
K. Schaffner, Photochemically Generated Building Blocks
M. Demuth, Natural Product Synthesis by Photochemical Methods
Synthesis of Enantiomerically Pure Compounds with
C,C Bond Formation:
D. Seebach - via Acetals and Enamines
G. Helmchen - by Asymmetric Diels - Alder Reactions
H. C. Brown - via Chiral Organoboranes
1986 Springer-Verlag Berlin Heidelberg
MODERN
SYNTHETIC
METHODS
1989
Biotransformations in Organic Synthesis
D. H. G. Crout and M. Christen
Enantioselective Catalysis with Metal Complexes
R. N oyori and M. Kitamura: an Overview
A. Pfaltz: Chiral Co- and Cu-Complexes
Aluminosilicates in Organic Synthesis
1. M. Thomas and Ch. R. Theocharis: Clays,
Zeolites and Other Microporous Solids for
Organic Synthesis
Springer-Verlag
Berlin Heidelberg New York
London Paris Tokyo
Prof. Dr. RolfScheffold
Institut fur organische Chemie der
Universitiit Bern
FreiestraBe 3
CH·3012 Bern
Copyrighl © Cover Design by Vedag Sauerllinder, Aarau/Schweiz
ISBN-) 3:978·3-540·5) 060-4 e-ISBN·) 3:978-3·642·83158-6
DOl: 10.1007/978-3-642-83758-6
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C Springer-Verlag Berlin Heidelberg 1989
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PREFACE
This paperback is the conference documentation of the fifth Seminar
on MODERN SYNTHETIC METHODS 1989. It is the aim of these triennial
Interlaken-Seminars to provide a proper, concine and "ready for use"
acceos to important and rapidly developing areas of synthetic
organic chemistry.
Usefu.l synthetic methods have to combine economic and ecological
aspects. The search for such methods is a continuous scientific
challenge. It implies a solid knowledge a~d updated information
on current prospects in biochemistry, organic as well as inorganic
chemiotry.
The main themes of the 1989-Seminar are "Biotransformations in
Organic Synthesis", "Enantioselective Catalyois with Metal Complexes"
and "Aluminosilicates in Organic Synthesis". These topics have been
chosen, since they reflect the enormous progress in experience and
understanding of catalysis in organic syntheGis.
This book if' the compilation of the contributions provided by the
lecturers of the Seminar. The reviews are written by leading experts
and describe not only the basic concepts, their application in
oynthesis but also contain representative experimental procedures.
The purpose of this volume is twofold. It should aid participants
and students in followi~g the lectures. The main reason, however,
is to serve ao an updated guide for chemists interested in catalyois
applied to organic synthesis.
Bern, 31th January 1989 Rolf Scheffold
CONTENTS
BIOTRANSFORMATIONS IN ORGANIC SYNTHESIS 1
I,., I.' I I" I. I I I 1'" I' I
David H.G. Crout and Markus Christen
Department of Chemistry, University of Warwick,
Coventry CV4 7AL, England
ENANTIOSELECTIVE CATALYSIS WITH METAL COMPLEXES, AN OVERVIEW .. 115
Ryoji Noyori and Masato Kitamura
Department of Chemistry, Nagoya University
Chikusa, Nagoya 464, Japan
ENANTIOSELECTIVE CATALYSIS WITH CHIRAL CO- AND CU-COMPLEXES ... 199
Andreas Pfa ltz
Ldboratorium fUr Organische Chemie der ETH-ZUrich
ETH-Zentrum, CH-8092 ZUrich, Switzerland
CLAYS, ZEOLITES AND OTHER MICROPOROUS SOLIDS
FOR ORGANIC SYNTHESIS ......................................... 249
John M. Thomas
Davey Faraday Research Laboratory,
The Royal Institution of Great Britain,
21, Albemarle Street,
Lonnon, WIX 46S, UK.
and
Charis R. Theocharis
Department of Chemistry
Brunel, The University of West London,
Uxbridge, Middlesex, UB8 3PH, UK.
BIOTRANSFORMATIONS IN ORGANIC SYNTHESIS
David H.G. Crout and Markus Christen
(Department of Chemistry, University of Warwick, Coventry CV4 7AL, England).
1.1 Introduction. 3
I I I'" t •• I I I ••• I 1,1" I 1'1' I I •• I I I
1.2 Applications ., 4
t •• I ••• , •• I • , • I I •• I •• I • , I I • 'I
1.3 Ground Rules in Biotransformations. ........... 4
1.4 Scope of Biotransformation Reactions.·.......... 5
1.5 Where to Start. 6
I I •••• I I I ••• I I • I , •• I , • • • • • • ••
2.1 Applications of Esterases, Lipases and
Prot eases. . ... 7
I • I • I I I ••• t I I • I I ••• , I I I •••••• I •• I
2.2 Esterase-catalysed Reactions. ..•..•.......•... 8
2.3 The "Meso Trick". ...•....................... 11
2.4 Kinetic Factors. ................•............ 17
2.5 Applications of Lipases. ...................•.. 18
2.6 Lipase-catalysed Resolutions. ..•......•....... 19
2.7 Enzymes in Low-water Systems. . . . . . . . . . . . . . .. 23
2.8 Applications of Proteases. . ...•..•............ 28
2.9 Regioselective Reactions of Lipases and
Proteases .. 32
I • I I , I , ••• f I I , •• I • I ••• I I • , •• It. I.
2.10 Lactone Formation and Hydrolysis. . . . . . . . . • . . .. 38
2.11 Microbial Hydrolyses .•....................... 39
2.12 Mild Methods. .•........................•... 41
2.13 Applications of Enzymes of Phosphate
Metabolism. . 42
I I I I I It •• I I I •• , I I •• I • I I • I I I I .,
2.14 Applications of Enzymes of Phosphate
Metabolism in Stereoselective Reactions. ........ 43
2.15 Applications of Enzymes in the Synthesis of
Phosphate Esters. .........•.....•.......•... 44
3.1 Biotransformations with Redox Enzymes. ......• 48
3.2 Applications of Dehydrogenases. .............•. 48
3.3 Dehydrogenases in Whole Cells. .....••...•.... 54
3.4 Oxygenases ... 67
I I I ••••• , I •• I I I I • I , , , •• I I • I •••
3.5 Biotransformations with Dioxygenases. ...•.••.. 68
3.6 Biotransformations with Monooxygenases. ..•..• 69
3.7 Oxidases. 71
1.,1.1.1 I ••• , 1.111 ••••• I ••••••• 1.1
R. Scheffold (Ed.)
Modern Synthetic Methods 1989, Vol. 5
© Springer-Verlag Berlin Heidelberg 1989
2
4.1 Synthesis of Amino Acids, Amides and
Peptides. . ..................................... 72
4.2 Hydrolysis of Nitriles and Hydantoins. ............ 72
4.3 Peptide Synthesis. .......................••...• 74
4.4 Peptide Synthesis in Low-water Systems. ......•.. 79
4.5 Applications of Polyethyleneglycol-modified
Enzymes. ..........................••....•••. 80
4.6 Protease- and Lipase-catalysed Reactions in
Low-water Systems. .......•....•.........•.... 80
4.7 Applications of Reverse Micelles. ................ 81
5.1 Enzyme-catalysed Synthesis of Glycosides
and Oligosaccharides. ............................ 82
6.1 Biotransformations Involving Carbon-Carbon
Bond Formation and Cleavage. 87
6.2 Biotransformations Using Aldolase. .......•....... 87
6.3 Biotransformations Using Transketolase. ..•....... 91
6.4 Acyloin Condensations Catalysed by Baker's
Yeast. •..........•........................•.. 93
6.5 Applications of Mandelonitrile Benzaldehyde
Lyase (Oxynitrilase). .....•....•......•......•.. 95
6.6 Applications of Acetolactate Decarboxylase. 95
7 Applications of Lyases. ........................... 96
8 Multiple Solutions to Synthetic Problems. 97
9 Future Developments. 100
Appendix: Suppliers of Enzymes. 101
References. 101
,. I I I I I I I. I. I I I I I I I I., I I I I I I "1 1'1 I I '" I I I I
3
1.1 Introduction.
A discussion of the application of biotransformations in organic
synthesis requires a definition of the term. For our present purposes,
biotransformations are:
"Selective enzymatic conversions of natural or chemically synthesised
substrates into defined products on a preparative scale using whole cells or
isolated enzyme systems"
Many review articles have been written' on biotransformations,
describing a very wide range of applications. However, the newcomer to the
field might well feel bewildered by the plethora of methods and techniques
available. A major objective of this chapter, therefore, is to highlight the most
widely used methods to be found in the literature, so that the routes most
widely trodden up until the present will become clear. It is hoped that in this
way to provide guidance on such questions as:
"To which problems in synthesis are biotransformations most likely to
provide a solution?"
"Should I use isolated enzymes or whole cells?"
"Which is the preferred class of enzyme or microorganism for my
particular problem?"
"Which particular enzyme or microorganism should I try first?"
"What method should I use for carrying out the reaction?"
Another aspect of biotransformations that sometimes inhibits
an organic chemists from investigating a biotransformation solution to a
synthetic problem, is his apprehension about handling a biological system.
However, as will become clear, many of the methods applied, particularly where
isolated enzymes are concerned, are little different in their execution from
"normal" chemical reactions. At the same time, it is undoubtedly an advantage
at least to have an acquaintance with basic biochemistry, and with basic
enzymology in particular. Because the field of biotransformation crosses borders
between scientific disciplines, it is also true that applications benefit greatly
from collaboration between chemists on the one hand, and biochemists and
microbiologists on the other. However, the lack of such collaborative support
need not deter the chemist from exploring the field. If he steps into it, not only
will he find that it is highly rewarding in providing him with valuable synthetic
procedures, but he will also havc the excitement that the added dimension of
handling a biological system brings.
However, one attribute of biotransformations will quickly
become evident, and that is the absence, for many systems, of the type of
ground rule that the study of mechanism has brought to classical organic
synthesis. Many of the biological systems used in biotransformation work are
treated as "black boxes". One of the great needs in this area is for there to be a
much better fundamental understanding of the properties of the enzymes and
microorganisms used. In the following account, therefore, the reader will
4
probably find himself asking frequently why a particular system should behave
in the way it does, without receiving a satisfactory answer. To this extent, many
of the applications have empirical aspects. This is very evident when, for
example, developments in the applications of enzymes in organic solvents are
considered. Many aspects of the behaviour of such sytems are extremely
puzzling, but the advantages that come from their use are so compelling that the
lack at present of even a rudimentary understanding of how they work should
not deter us from applying them.
1.2 Applications.
A most important preliminary to using biotransformations is to
be clear about the kind of application in which they are most relevant. They
may be listed as follows.
1. The main impetus for biotransformation studies has been the
continued growth in the demand for enantiomerically pure
compounds. The great majority of applications have this goal as their
primary objective. Biotransformations in this category rely on the
high stereoselectivity exhibited by enzymes with respect to
substrates and the stereospecificity of the reactions catalysed.
2. Advantage is often taken of the regioselectivity of enzyme-catalysed
reactions. Examples can be found in the selective esterification of
dicarboxylic acids, the selective hydrolysis of compounds containing
multiple ester functions (dicarboxylic acid esters, sugar esters etc)
and the selective reduction of compounds containing multiple
carbonyl groups. Examples of all of these are given in later sections.
3. There is a continued and growing interest in the application of
enzymes in areas of synthesis where they offer certain advantages
over chemical procedures. Examples include peptide synthesis and
oligosaccharide synthesis. The latter area presents many major
challenges to the organic chemist. Biotransformation procedures are
being applied in this field with increasing frequency and many
possibilities exist for further developments.
4. Enzymatic methods are characterised by their mildness. Therefore
they can be applied usefully in cases where either substrates or
products of reactions are chemically' labile.
The synthetic chemist might therefore look towards a
biotransformation solution for problems in any of the categories 1 to 4, above.
1.3 Ground Rules in Biotransformations.
The great power of biotransformations as a synthetic tool in
certain defined areas will become evident in the following account. However, as