Ruthenium Oxidation Complexes: Their Uses as Homogenous Organic Catalysts

275 Pages·2011·4.52 MB·English

by  William P. Griffith (auth.)

Ruthenium Oxidation Complexes
Catalysis by Metal CoMplexes
This book series covers topics of interest to a wide range of academic and industrial
chemists, and biochemists. Catalysis by metal complexes plays a prominent role in
many processes. Developments in analytical and synthetic techniques and instru-
mentation, particularly over the last 30 years, have resulted in an increasingly
sophisticated understanding of catalytic processes.
Industrial applications include the production of petrochemicals, fine chemicals
and pharmaceuticals (particularly through asymmetric catalysis), hydrometallurgy,
and waste-treatment processes. Many life processes are based on metallo-enzyme
systems that catalyse redox and acid-base reactions.
Catalysis by metal complexes is an exciting, fast developing and challenging
interdisciplinary topic which spans and embraces the three areas of catalysis:
heterogeneous, homogeneous, and metallo-enzyme.
Catalysis by Metal Complexes deals with all aspects of catalysis which involve
metal complexes and seeks to publish authoritative, state-of-the-art volumes which
serve to document the progress being made in this interdisciplinary area of science.
Series Editors
Prof. Claudio Bianchini Prof D. J. Cole-Hamilton
Institute of Chemistry of Organometallic Compounds, EaStCHEM School of
Polo Scientifico Area Chemistry
Via Madonna del Piano 10 University of St Andrews
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Tarragona 43007
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Former Series Editor
Brian R. James, University of British Columbia, Vancouver, Canada
Editor of this series from 1976–2009
Brain R. James played a significant editorial role in the realization of this volume
VoluMe 34:
RutheniuM oxidation CoMplexes
Volume Author
W.P. Griffith
Department of Chemistry
Imperial College
London, SW7 2AZ
United Kingdom
For other titles published in this series,
go to http:// www.springer.com/series/5763
Prof. William P. Griffith
Ruthenium Oxidation
Complexes
Their Uses as Homogenous Organic Catalysts
Prof. William P. Griffith
Department of Chemistry
Imperial College
London, SW7 2AZ
United Kingdom
[email protected]
ISBN 978-1-4020-9376-0 e-ISBN 978-1-4020-9378-4
DOI 10.1007/978-1-4020-9378-4
Springer Dordrecht New York Heidelberg London
Library of Congress Control Number: 2010935300
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preface
This book is concerned with the application of ruthenium complexes as catalysts
for useful organic oxidations.
Ruthenium was the last of the platinum-group elements to be discovered, and
has perhaps the most interesting and challenging chemistry of the six. In this book
just one major aspect is covered: its ability, mainly by virtue of its remarkably wide
range of oxidation states which exist in its many complexes (from +8 to −2 inclu-
sive) to effect useful and efficient oxidations of organic substrates.
Emphasis has been placed on useful organic oxidations, particularly on the cata-
lytic production of natural products or pharmaceuticals and of the oxidation of
important organic functional groups such as alcohols, alkenes, alkynes, amines and
heteroatomic functionalities. The book is not directed solely at organic chemists. It
is hoped that the inorganic, organometallic and coordination chemist will draw
from it useful information, particularly from Chapter 1. The coverage of this very
large subject can not claim to be entirely comprehensive, but it is hoped that all the
main references, including some from 2010, have been covered.
The first chapter concerns the chemistry of the oxidation catalysts, some 250 of
these, arranged in decreasing order of the metal oxidation state (VIII) to (0).
Preparations, structural and spectroscopic characteristics are briefly described, fol-
lowed by a summary of their catalytic oxidation properties for organic substrates,
with a brief appendix on practical matters with four important oxidants. The subse-
quent four chapters concentrate on oxidations of specific organic groups, first for
alcohols, then alkenes, arenes, alkynes, alkanes, amines and other substrates with
hetero atoms. Frequent cross-references between the five chapters are provided.
I would like to thank my good friend Brian James of the University of British
Columbia (UBC), who suggested some years ago that I write a book of this type
and who has carefully read and trenchantly criticised large sections of it. From
Imperial College I am deeply indebted to Ed Smith who has read all of it and
pointed out a number of errors and inconsistencies, and Ed Marshall who has drawn
all the figures. I am very grateful to Steve Ley from Cambridge who has read the
section on TPAP, the reagent which he, I and our co-workers developed. Any
remaining errors and omissions are entirely my responsibility. All the cited refer-
ences have of course been consulted and, though most are from online sources, it
v
vi Preface
is a pleasure to thank the librarians of Imperial College, the Science Museum and
the Royal Society of Chemistry libraries, and of course of the British Library.
Finally, I am deeply grateful to my wife Anne (and in earlier years to my daughters
Helen and Miranda) for her forbearance during the long time this book has taken to
compile.
Contents
1 the Chemistry of Ruthenium oxidation Complexes ........................... 1
1.1 Overview and Introduction ................................................................ 1
1.1.1 Discovery of Ruthenium ........................................................ 3
1.1.2 Oxidation States in Ruthenium Complexes ........................... 3
1.1.3 Reviews on Ruthenium Complexes
in Oxidation Reactions ........................................................... 4
1.1.4 Reviews on Oxidations of Organic Substrates
by Ru Complexes ................................................................... 4
1.1.5 Syntheses of Natural Products or Pharmaceuticals
by Ru Catalysts ...................................................................... 5
1.2 Ru(VIII) Complexes ........................................................................... 7
1.2.1 Ruthenium Tetroxide, RuO ................................................... 7
4
1.2.2 Preparation ............................................................................. 7
1.2.3 Physical Properties ................................................................. 8
1.2.4 Analysis and Toxicity ............................................................. 10
1.2.5 RuO as an Organic Oxidant .................................................. 11
4
1.2.6 Co-oxidants and Solvents for RuO Oxidations ..................... 12
4
1.2.7 Oxidations Effected by RuO ................................................. 14
4
1.2.8 Other Ru(VIII) Complexes..................................................... 30
1.3 Ru(VII) Complexes ............................................................................ 30
1.3.1 Perruthenates, TPAP and [RuO]− .......................................... 30
4
1.3.2 Preparation ............................................................................. 31
1.3.3 Physical Properties ................................................................. 32
1.3.4 TPAP and [RuO]− as Organic Oxidants ................................ 33
4
1.3.5 Other Ru(VII) Species............................................................ 40
1.4 Ru(VI) Complexes ............................................................................. 40
1.4.1 Ruthenates, [RuO]2− .............................................................. 41
4
1.4.2 Ru(VI) Complexes Containing Dioxo Moieties..................... 47
1.4.3 Ru(VI) Complexes Containing Mono-Oxo
or Nitride Donors ................................................................... 66
vii
viii Contents
1.5 Ru(V) Complexes. .............................................................................. 67
1.6 Ru(IV) Complexes ............................................................................. 69
1.6.1 Ruthenium Dioxide, RuO and RuO.nHO ........................... 70
2 2 2
1.6.2 Ru(IV) Complexes with O- or N-Donors ............................... 71
1.7 Ru(III) Complexes.............................................................................. 76
1.7.1 Ru(III) Complexes with O-Donors ........................................ 76
1.7.2 Ruthenium Trichloride, RuCl and RuCl.nHO .................... 79
3 3 2
1.7.3 RuBr and Halo-Aqua Complexes ......................................... 83
3
1.7.4 Ru(III) Complexes with Chelating O-, N-Donors .................. 83
1.7.5 Ru(III) Complexes with N-Donors ........................................ 85
1.7.6 Ru(III) Complexes with -P, -As, -Sb
and -S Donors ......................................................................... 88
1.8 Ru(II–III) Complexes ......................................................................... 89
1.9 Ru(II) Complexes ............................................................................... 89
1.9.1 Ru(II) Complexes with O- and N-Donors .............................. 90
1.9.2 Ru(II) Complexes with Porphyrin, Phthalocyanine
and Macrocyclic Donors ........................................................ 95
1.9.3 Ru(II) complexes with -P, -As and -Sb Donors ...................... 97
1.9.4 Ru(II) Complexes with -S and -O Donors ............................. 105
1.9.5 Ru(II) Complexes with -C Donors ......................................... 108
1.10 Ru(0) Complexes................................................................................ 110
1.11 Appendix: Brief Resumé of Preparations of Ru Oxidants
and Oxidation Reactions .................................................................... 110
1.11.1 Preparations of RuO In Situ for Oxidations ........................ 110
4
1.11.2 Preparations and Use of [RuO]− .......................................... 111
4
1.11.3 Preparations and Use of [RuO]2− ......................................... 112
4
1.11.4 Preparation of trans-Ru(O)(bpy)
2
{IO(OH)}1.5HO ............................................................... 113
3 3 2
References ......................................................................................................... 113
2 oxidation of alcohols, Carbohydrates and diols ................................... 135
2.1 Primary Alcohols to Aldehydes (Table 2.1) ....................................... 136
2.1.1 Model Substrates .................................................................... 137
2.1.2 Specific Examples .................................................................. 137
2.1.3 Natural Product/Pharmaceutical Syntheses
Involving Primary Alcohol Oxidations .................................. 139
2.2 Primary Alcohols to Carboxylic Acids (Table 2.1) ............................ 141
2.2.1 Model Substrates .................................................................... 141
2.3 Secondary Alcohols to Ketones or Lactones...................................... 142
2.3.1 Model Substrates .................................................................... 142
2.3.2 Specific Examples .................................................................. 145
2.3.3 Natural Product/Pharmaceutical Syntheses
Involving Secondary Alcohol Oxidations .............................. 146
2.3.4 Hydroxylactones, a-Hydroxy Esters and Cyanohydrins ....... 148
2.3.5 Deracemisation of Secondary Alcohols ................................. 148
Contents ix
2.3.6 Alcohols, Carbohydrates and Diols Not Covered
Here but Included in Chapter 1 .............................................. 149
2.3.7 Large-Scale Oxidations of Alcohols, Carbohydrates
and Diols ................................................................................ 150
2.4 Carbohydrates .................................................................................... 151
2.4.1 Primary Alcohol Groups in Carbohydrates
to Carboxylic Acids................................................................ 152
2.4.2 Secondary Alcohol Groups in Carbohydrates
to Ketones ............................................................................... 153
2.4.3 Syntheses of Carbohydrate Natural Products/
Pharmaceuticals...................................................................... 159
2.4.4 Miscellaneous Carbohydrate Oxidations ............................... 160
2.5 Diols ................................................................................................... 160
2.5.1 Specific Examples .................................................................. 160
2.5.2 Natural Product/Pharmaceutical Syntheses
Involving Diols ....................................................................... 161
2.5.3 Desymmetrisation of Meso-Diols .......................................... 162
2.6 Miscellaneous Oxidations of Alcohols .............................................. 162
References ......................................................................................................... 163
3 oxidation of alkenes, arenes and alkynes ........................................... 173
3.1 Oxidation of Alkenes Involving No C=C Bond Cleavage ................. 173
3.1.1 Epoxidation of Cyclic and Linear Alkenes ............................ 174
3.1.2 Cis-Dihydroxylation of Alkenes ............................................ 181
3.1.3 Ketohydroxylations ............................................................... 185
3.2 Oxidative Cleavage of Alkenes .......................................................... 192
3.2.1 Alkene Cleavage to Aldehydes or Ketones ............................ 192
3.2.2 Alkene Cleavage to Carboxylic Acids ................................... 196
3.3 Oxidation of Arenes ........................................................................... 200
3.3.1 Aromatic Rings to Carboxylic Acids or to CO ..................... 201
2
3.3.2 Phenols ................................................................................... 203
3.3.3 Polycyclic Arenes ................................................................... 203
3.3.4 Oxidative Coupling of Arenes and Napththols ...................... 204
3.3.5 Large-Scale Oxidations of Arenes ......................................... 204
3.3.6 Aromatic Substrates Not Covered Here
but Included in Chapter 1 ....................................................... 204
3.4 Oxidation of Alkynes ......................................................................... 205
3.4.1 Oxidation of Alkynes Involving No
C=C Bond Cleavage ............................................................... 205
3.4.2 Oxidative Cleavage of Alkynes to Carboxylic Acids ............. 206
References ......................................................................................................... 207
4 oxidation of alkanes ................................................................................ 215
4.1 Oxidation of C–H Bonds in Alkanes ................................................. 215
4.1.1 Aldehydes and Other R1R2R3CH Substrates .......................... 215