Handbook of Reagents for Organic Synthesis: Acidic and Basic Reagents

591 Pages·1999·38.39 MB·English

by  Hans J. Reich

Handbook of Reagents
for Organic Synthesis
Acidic and Basic Reagents
Edited by
Hans J. Reich
The University of Wisconsin at Madison
and
James H. Rigby
Wayne State University
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Editorial Board
Editor-in-Chief
Leo A. Paquette
The Ohio State University, Columbus, OH, USA
Editors
Steven D. Burke Robert M. Coates Rick L. Danheiser
University of Wisconsin University of Illinois Massachusetts Institute of
at Madison, WI, USA at Urbana-Champaign, IL Technology, Cambridge, MA,
USA USA
Scott E. Denmark
University of Illinois David J. Hart Lanny S. Liebeskind
at Urbana-Champaign, IL, The Ohio State University Emory University
USA Columbus, OH, USA Atlanta, GA, USA
Dennis C. Liotta Anthony J. Pearson Hans J. Reich
Emory University Case Western Reserve University of Wisconsin
Atlanta, CA, USA University, Cleveland, OH, USA at Madison, WI, USA
James H. Rigby William R. Roush
Wayne State University University of Michigan
Detroit, MI, USA MI, USA
Assistant Editors
James P. Edwards Mark Volmer
Ligand Pharmaceuticals Emory University
San Diego, CA, USA Atlanta, GA, USA
International Advisory Board
Leon A. Ghosez Jean-Marie Lehn Steven V. Ley
Université Catholique Université Louis Pasteur University of Cambridge
de Louvain, Belgium Strasbourg, France UK
Chun-Chen Liao Lewis N. Mander Giorgio Modena
National Tsing Hua Australian National Università di Padua
University, Hsinchu, Taiwan University, Canberra Italy
Australia
Ryoji Noyori
Edward Piers
Nagoya University, Japan
Gerald Pattenden University of British
Pierre Potier University of Nottingham Columbia, Vancouver
CNRS, Gif-sur-Yvette UK Canada
France
W. Nico Speckamp Ekkehard Winterfeldt
Hishashi Yamomoto Universiteit van Amsterdam Universität Hannover
Nagoya University, Japan The Netherlands Germany
Managing Editor
Colin J. Drayton
Woking, Surrey, UK
Contents
Preface ix Diethylaluminum Chloride 132
Diisopropylethylamine 134
Introduction xi
Dimethylaluminum Chloride 137
Organic Synthesis Examples 1
4-Dimethylaminopyridine 140
Recent Review Articles and Monographs 6 Esterases 143
Ethylaluminum Dichloride 146
Alumina 9 Fluorosulfuric Acid-Antimony(V) Fluoride 151
Aluminum Chloride 12 Formic Acid 155
Aluminum Isopropoxide 16 Hexamethyldisilazane 158
Antimony(V) Fluoride 19 Hexamethylphosphoric Triamide 160
Barium Hydroxide 24 Hexamethylphosphorous Triamide 166
Benzyltrimethylammonium Hydroxide 27 Hydrazine 169
(R)-l,l'-Bi-2,2'-naphthol 29 Hydrobromic Acid 173
(R)-1,l'-Bi-2,2'-naphthotitanium Dichloride Hydrochloric Acid 178
(and Dibromide) 35 Hydrogen Bromide 183
Hydrogen Chloride 185
(R) and (S)-2,2'-Bis(diphenylphosphino)-l,l'-binaphthyl 38
Bis(tri-n-butyltin) Oxide 42 Hydrogen Fluoride 187
Boron Tribromide 44 Hydrogen Iodide 190
Boron Trichloride 47 Imidazole 194
Boron Trifluoride Etherate 50 Iron(III) Chloride 195
Bromodimethylborane 59 Lipases 199
Bromomagnesium Diisopropylamide 61 Lithium Amide 204
Brucine 63 Lithium Bromide 207
n-Butyllithium 66 Lithium t-Butoxide 208
s-Butyllithium 74 Lithium Carbonate 209
t-Butyllithium 81 Lithium Chloride 210
n-Butyllithium-Potassium t-Butoxide 86 Lithium Diethylamide 211
Calcium Carbonate 88 Lithium Diisopropylamide 213
Lithium Hexamethyldisilazide 221
Calcium Hydride 89
10-Camphorsulfonic Acid 91 Lithium Hydroxide 224
Cerium (III) Chloride 94 Lithium Iodide 227
Cesium Carbonate 97 Lithium N-Methylpiperazide 228
Lithium Perchlorate 229
Cesium Fluoride 99
Lithium Tetrafluoroborate 231
2,4,6-Collidine 104
Lithium 2,2,6,6-Tetramethylpiperidide 232
Copper(I) Trifluoromethanesulfonate 105
2,6-Lutidine 235
Copper(II) Trifluoromethanesulfonate 116
18-Crown-6 118 Magnesium Bromide 237
l,5-Diazabicyclo[4.3.0]non-5-ene 123 Magnesium Methoxide 239
1,8-Diazabicyclo[5.4.0]undec-7-ene 125 Mercury(II) Acetate 240
2,6-Di-t-butylpyridine 131 Mercury(II) Chloride 246
viii CONTENTS
Mercury(II) Trifluoroacetate 248 Sodium Hydroxide 343
Mesityllithium 251 Sodium Methylsulfinylmethylide 344
Methanesulfonic Acid 252 (—)-Sparteine 350
Methylaluminum Sulfur Dioxide 352
Bis(2,6-di-t-butyl-4-methylphenoxide) 254 Sulfuric Acid 357
Methylaluminum Bis(2,6-di-t-butylphenoxide) 257 Sulfur Trioxide 360
Methylaluminum Dichloride 258 Tetra-n-butylammonium Fluoride 364
Molecular Sieves 259 Tetra-n-butylammonium Hydroxide 367
Montmorillonite K10 262 Tetrafluoroboric Acid 368
Nitric Acid 266 Tetrahydro-l-methyl-3,3-diphenyl-lH,3H-
Phosphazene Base P-t-Bu 270 pyrrolo[1,2-c] [1,3,2]oxazaborole 372
4
Phosphoric Acid 272 N,N,N',N'-Tetramethylethylenediamine 376
Phosphorus(V) Oxide-Methanesulfonic Acid 273 1,1,3.3-Tetramethylguanidine 380
Polyphosphate Ester 277 Tin(IV) Chloride 383
Polyphosphoric Acid 279 Tin(II) Trifluoromethanesulfonate 389
Potassium Amide 285 Titanium(IV) Chloride 392
Potassium 3-Aminopropylamide 288 Titanium Tetraisopropoxide 398
Potassium t-Butoxide 290 p-Toluenesulfonic Acid 402
Potassium Carbonate 296 Tri-n-butyl(methoxy)stannane 405
Potassium Diisopropylamide 298 Tri-n-butyltin Trifluoromethanesulfonate 409
Potassium Fluoride 300 Triethylamine 410
Potassium Hexamethyldisilazide 303 Triethyl Phosphite 415
Potassium Hydride 307 Trifluoroacetic Acid 419
Potassium Hydroxide 310 Trifluoromethanesulfonic Acid 421
Propionic Acid 313 Trimethyl Phosphite 425
Pyridine 314 Trimethylsilyl Trifluoromethanesulfonate 427
Pyridinium p-Toluenesulfonate 318 Triphenylarsine 431
Pyrrolidine 319 Triphenylcarbenium Tetrafluoroborate 434
Quinine 322 Zinc Bromide 437
Quinoline 324 Zinc Chloride 440
Silver(I) Tetrafluoroborate 327 Zinc Iodide 448
Sodium Amide 329
Sodium Carbonate 333 List of Contributors 451
Sodium Ethoxide 334 Reagent Formula Index 459
Sodium Hexamethyldisilazide 338 Subject Index 463
Sodium Hydride 340
Preface
As stated in its Preface, the major motivation for our under­ Reagents, Auxiliaries and Catalysts for C-C Bond
taking publication of the Encyclopedia of Reagents for Formation
Organic Synthesis was "to incorporate into a single work Edited by Robert M. Coates and Scott E. Denmark
a genuinely authoritative and systematic description of the
Oxidizing and Reducing Agents
utility of all reagents used in organic chemistry." By all
Edited by Steven D. Burke and Rick L. Danheiser
accounts, this reference compendium has succeeded admir­
ably in attaining this objective. Experts from around the Acidic and Basic Reagents
globe contributed many relevant facts that define the var­ Edited by Hans J. Reich and James H. Rigby
ious uses characteristic of each reagent. The choice of a
Activating Agents and Protecting Groups
masthead format for providing relevant information about
Edited by Anthony J. Pearson and William R. Roush
each entry, the highlighting of key transformations with
illustrative equations, and the incorporation of detailed
Each of the volumes contains a complete compilation of
indexes serve in tandem to facilitate the retrieval of desired
those entries from the original Encyclopedia that bear on
information.
the specific topic. Ample listings can be found to function­
Notwithstanding these accomplishments, the editors have
ally related reagents contained in the original work. For the
since recognized that the large size of this eight-volume
sake of current awareness, references to recent reviews and
work and its cost of purchase have often served to deter
monographs have been included, as have relevant new pro­
the placement of copies of the Encyclopedia in or near
cedures from Organic Syntheses.
laboratories where the need for this type of insight is most
The end product of this effort by eight of the original
critically needed. In an effort to meet this demand in a cost-
editors of the Encyclopedia is an affordable, enlightening
effective manner, the decision was made to cull from the
set of books that should find their way into the laboratories
major work that information having the highest probability
of all practicing synthetic chemists. Every attempt has been
for repeated consultation and to incorporate same into a set
made to be of the broadest synthetic relevance and our
of handbooks. The latter would also be purchasable on a
expectation is that our colleagues will share this opinion.
single unit basis.
The ultimate result of these deliberations is the publica­
tion of the Handbook of Reagents for Organic Synthesis Leo A. Paquette
consisting of the following four volumes: Columbus, Ohio USA
Introduction
Recognizing the critical need for bringing a cost effective Acids and bases are among the most fundamental and
as well as handy reference work dealing with the most versatile reagents for effecting organic transformations,
popular reagents in synthesis to the widest possible audi­ and in selecting candidate entries for inclusion in this par­
ence of practicing organic chemists, the editors of The ticular collection, the editors adopted a fairly broad set of
Encyclopedia of Reagents for Organic Synthesis (EROS) criteria for defining what exactly constitutes an acidic or
have developed a list of the most important and useful basic reagent. Therefore, not only are the usual acids and
reagents employed in contemporary organic synthesis. The bases such as hydrochloric acid, aluminum chloride, potas­
result of this effort is a collection entitled "Handbook of sium t-butoxide and so forth included, so are compounds
Reagents for Organic Synthesis" that contains over 500 that behave like acids or bases but that are normally clas­
reagent entries from the original Encyclopedia that run sified in other ways. For instance, articles on ligands or
the gamut of functions from oxidation and reduction to complexing agents such as 18-crown-6, l,l'-bi-2,2'-
activation and protection. To assist the reader in quickly naphthol and triethylphosphite can also be found in this
locating a reagent of interest, the "Handbook" has volume along with the more traditional Bronsted/Lewis
been divided into four volumes, each of which is devoted acids and bases. Furthermore, in recognition of the growing
to a set of closely related reagents, these include: importance of biocatalysts in the field of organic synthesis,
articles on esterases and lipases are also included in this
"Reagents, Auxiliaries and Catalysts for C-C Bond Forma­
volume since, in the broadest sense, the net conversions
tion"; "Oxidizing and Reducing Agents"; "Acidic
effected by these enzymes can be viewed as being of an
and Basic Reagents"; Activating Agents and Protecting
acidic or basic nature.
Groups".
Compiled in the present volume, entitled "Acidic and In compiling the master list of reagents to be included in
Basic Reagents," is a group of articles on the most useful the "Handbook" the editors endeavored to consider not
and important acidic and basic agents that were originally only species of the broadest current synthetic importance
included in the very popular Encyclopedia of Reagents for and accepted utility, but also reagents that may not yet be
Organic Synthesis. Each article contains all of the informa­ fully integrated into mainstream synthetic practice, but will
tion found in the original version as well as extensive list­ certainly become so in the future. A good example of this is
ings of functionally related reagents that are located in the the entry on the very potent, but little used, phosphazene
full Encyclopedia. Following this Introduction are listings base P4-t-Bu, one of the so-called Schwesinger bases,
of Recent Review Articles and Monographs on subjects which the editors believe will become, in the fullness of
related in a general sense to the topic of acids and bases as time, a more broadly used reagent. A number of reagents
well as relevant Organic Syntheses that deal with either present in this four volume series were identified as exhi­
the preparations or reactions of reagents featured in this biting multiple applications that could have simultaneously
volume. To make this work as up to date as possible, par­ placed them appropriately in several different volumes. To
avoid unnecessary duplication, articles describing these
ticular emphasis was placed on including references appear­
types of reagents were assigned to a single volume and
ing since the original publication date of EROS in 1995. It
only cross references to these particular entries are included
is hoped that by including these listings, the reader will be
in the other relevant volumes. For example, the entry for
able to quickly access a broad range of information of
ethylaluminum dichloride is found in the volume entitled
interest that is beyond the scope of the reagent entries
"Activating Agents and Protecting Groups" with only a
themselves.
xii INTRODUCTION
"boiler plate" cross reference listing in this volume. Simi­ and most important acidic and basic reagents to be a valu­
larly, hexamethyldisilazane can serve as a base in some able addition to your chemical library.
instances, but it can also be employed to transfer Me Si
3
and, as such, will be found in the volume focusing on Hans J. Reich
"Activating Agents and Protecting Gruops". The University of Wisconsin at Madison
The editors of The Encyclopedia of Reagents for Organic James H. Rigby
Synthesis hope that you find this compilation of the best Wayne State University
List of Contributors
Ahmed F. Abdel-Magid The R. W. Johnson Pharmaceutical Research Institute, Spring House, PA, USA
• Barium Hydroxide 24
• Lithium Hydroxide 224
• Potassium Hydroxide 310
Benjamin A. Anderson Lilly Research Laboratories, Indianapolis, IN, USA
• Hexamethyldisilazane 158
Paul C. Anderson Bio-Méga/Boehringer Ingelheim Research, Laval, Quebec, Canada
Bromodimethylborane 59
William F. Bailey University of Connecticut, Storrs, CT, USA
• t-Butyllithium 81
Bert H. Bakker University of Amsterdam, The Netherlands
• Sulfur Trioxide 360
Wouter I. Iwema Bakker University of Waterloo, Ontario, Canada
• Lithium Diisopropylamide 213
Martin G. Banwell University of Melbourne, Parkville, Victoria, Australia
• Titanium Tetraisopropoxide 398
Albert K. Beck Eidgenossische Technische Hochschule, Zurich, Switzerland
• Mesityllithium 251
John L. Belletire The University of Cincinnati, OH, USA
• Sodium Amide 329
Joachim Berkner Georgia Institute of Technology, Atlanta, GA, USA
• 18-Crown-6 118
T. Howard Black Eastern Illinois University, Charleston, IL, USA
• Magnesium Bromide 237
Mary Ellen Bos The R. W. Johnson Pharmaceutical Research Institute, Raritan, NJ, USA
• Benzyltrimethylammonium Hydroxide 27
• Tetra-n-butylammonium Hydroxide 367
Bruce P. Branchaud University of Oregon, Eugene, OR, USA
• Cesium Fluoride 99
• Tetrafluoroboric Acid 368
Gary W. Breton University of North Carolina, Chapel Hill, NC, USA
• Hydrogen Bromide 183
• Hydrogen Chloride 185
Steven D. Burke University of Wisconsin, Madison, WI, USA
• Sulfur Dioxide 352
452 LIST OF CONTRIBUTORS
Drury Caine The University of Alabama, Tuscaloosa, AL, USA
• Magnesium Methoxide 239
• Potassium t-Butoxide 290
• Lithium t-Butoxide 208
Mike Campbell University of Waterloo, Ontario, Canada
• Lithium 2,2,6,6-Tetramethylpiperidide 232
Hans Cerfontain University of Amsterdam, The Netherlands
• Sulfur Trioxide 360
Andre B. Charette Université de Montreal, Quebec, Canada
• Lithium Bromide 207
• Lithium Iodide 227
• Lithium Perchlorate 229
Paul J. Coleman Indiana University, Bloomington, IN, USA
• Lithium Tetrafluoroborate 231
Daniel L. Comins North Carolina State University, Raleigh, NC, USA
• Lithium N-Methylpiperazide 228
Veronica Cornel Emory University, Atlanta, GA, USA
• Boron Trifiuoride Etherate 50
Robert Dahinden Eidgenössische Technische Hochschule, Zurich, Switzerland
• Mesityllithium 251
Kenneth G. Davenport Hoechst Celanese Corporation, Corpus Christi, TX, USA
• Hydrogen Fluoride 187
Arnold Davis University of Miami, Coral Gables, EL, USA
• Calcium Hydride 89
Kurt D. Deshayes Bowling Green State University, OH, USA
• Potassium Carbonate 296
• Sodium Hydroxide 343
Lisa A. Dixon The R. W. Johnson Pharmaceutical Research Institute, Raritan, NJ, USA
• Phosphorus(V) Oxide-Methanesulfonic Acid 273
• Polyphosphate Ester 277
John H. Dodd The R. W. Johnson Pharmaceutical Research Institute, Raritan, NJ, USA
• Polyphosphoric Acid 279
Robert R. Dykstra University of Wisconsin, Madison, WI, USA
• Hexamethylphosphoric Triamide 160
Thomas M. Eckrich Eli Lilly and Company, Lafayette, IN, USA
• Tri-n-butyltin Trifluoromethanesulfonate 409
Kirk F. Eidman Scios Nova, Baltimore, MD, USA
• Formic Acid 155
• Propionic Acid 313
• Trifiuoroacetic Acid 419
Ihsan Erden San Francisco State University, CA, USA
• Lithium Amide 204
Ronald H. Erickson Scios Nova, Baltimore, MD, USA
• Bromomagnesium Diisopropylamide 61