Lewis Acids in Organic Synthesis

1005 Pages·2000·24.31 MB·English

Johann Casteiger (Ed.)
Handbook of
Chemoinformatics
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Lewis Acids
in Organic Synthesis
Edited by Hisashi Yamamoto
@WILEY-VCH
Weinheim . New York . Chichester . Brisbane . Singapore . Toronto
Prof. Dr. H. Yamamoto
Graduate School of Engineering
Nagoya University, CREST (JST)
Furo-cho, Chikusa
Nagoya 464-8603
Japan
This book was carefully produced. Nevertheless, authors, editor and publisher do not warrant the
information contained therein to be free of errors. Readers are advised to keep in mind that state-
ments, data, illustrations, procedural details or other items may inadvertently be inaccurate.
1 st Edition 2000
1st Reprint 2002
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0W ILEY-VCH Verlag GmbH, D-69469 Weinheim (Federal Republic of Germany), 2000
ISBN 3-527-29579-8
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Preface
The designation of electron-pair donors and acceptors as Lewis bases and Lewis acids
is firmly and fittingly ingrained in the language of chemistry. G. N. Lewis laid the
foundation for this important theory approximately 80 years ago and Lewis acids have
since become increasingly important because of their central role in synthetic organic
chemistry. This is clearly illustrated by an ever-increasing number of publications and
books.
This volume focuses on different areas of Lewis acid chemistry, selected because they
have developed significantly and, in some cases, even completely in the last two decades.
Each is treated in more depth than would be possible in a volume that attempted to cover
all Lewis acid chemistry comprehensively. The authors are knowledgeable about the
area reviewed, have contributed to its development, and are uniquely able to provide
valuable perspectives. I was fortunate that these distinguished chemists were willing to
devote the time and effort required to write these contributions.
These chapters demonstrate the abundance of significant developments of Lewis
acid reagents and related areas. It is hoped that this handbook will serve as a catalyst
to encourage the dissemination of their (so far untapped) full potential in organic syn-
thesis throughout the twenty-first century.
Hisashi Yamamoto, Nagoya
Contents
Volume 1
Preface V
List of Authors XVII
1 Introduction
Hisashi Yamamoto 1
References 7
2 Li(I), Na(I), and K(1) Lewis Acids
Susumu Saito 9
2.1 Introduction 9
2.2 General Properties of Alkali Metal Salt 10
2.2.1 Lewis Acidic Properties of Alkali Metal Salt 10
2.2.2 Alkali Metal Halide Effect 17
2.3 Application to Synthetic Organic Chemistry 28
2.3.1 Cycloaddition Reactions 28
2.3.2 Substitution Reactions 39
2.3.3 Nucleophilic Addition to the C=O Double Bond 45
2.3.4 Conjugate Addition 47
2.3.5 Rearrangement 50
2.3.6 Oxirane Ring-Opening Functionalization 52
2.4 Closing Remarks 55
References 55
3 Mg(1I) and Zn(I1) Lewis Acids
YukihiroM otoyama and Hisao Nishiyama 59
3.1 Introduction 59
3.2 The Diels-Alder Reaction 59
3.2.1 Control of Diastereoselectivity 60
3.2.2 Chiral Lewis Acid Complexes 62
3.3 Radical-Mediated Reactions 67
3.3.1 Control of Diastereoselectivity 67
3.3.2 Asymmetric Reactions using Chiral Auxiliaries 69
VIII Contents
3.3.3 Enantioselective Reactions 71
3.4 Other Reactions 75
3.5 Concluding Remarks 85
References 85
4 Achiral B(II1) Lewis Acids
Kazuaki Ishihara 89
4.1 Introduction 89
4.2 H3B03-promoted Reactions 90
4.3 B13-, BBr3-, or BC13-promoted Reactions 91
4.3.1 Cleavage of Ethers, Acetals, and Esters 91
4.3.2 Glycosidation of Glycals 95
4.3.3 Synthesis of Organoboron Reagents 95
4.4 BF3-Promoted Reactions 96
4.4.1 Cleavage of Ethers 96
4.4.2 Friedel-Crafts Alkylation Reactions 97
4.4.3 Friedel-Crafts Acylation Reactions 98
4.4.4 Cyclizations 99
4.4.5 Rearrangement Reactions 101
4.4.6 Diels-Alder Reactions 104
4.4.7 Desilylation Reactions 106
4.4.8 Destannylation Reactions 107
4.4.9 Acylation Reactions of Ketones and Nitriles 107
4.4.10 Addition Reactions 109
4.4.11 Aldol Reactions 111
4.4.12 Miscellaneous Reactions 112
4.5 Arylboron Compounds as Lewis Acid Catalysts 114
4.5.1 Triarylboron 114
4.5.2 Diarylborinic Acid 121
4.5.3 Arylboronic Acid 126
4.6 Conclusions 130
References 130
5 Chiral B(II1) Lewis Acids
Kazuaki Zshihara 135
5.1 Introduction 135
5.2 Enantioselective Carbo Diels-Alder Reactions 135
5.2.1 Chiral Lewis Acids as Stoichiometric Reagents 135
5.2.2 Chiral Lewis Acids as Catalytic Reagents 137
5.3 Enantioselective Hetero Diels-Alder Reactions 160
5.4 Enantioselective Mukaiyama Aldol Reactions 162
5.4.1 Chiral Lewis Acids as Stoichiometric Reagents 163
5.4.2 Chiral Lewis Acids as Catalytic Reagents 169
5.5 Enantioselective Sakurai-Hosomi Allylation Reactions 176
5.6 Enantioselective Claisen Rearrangement 179
5.7 Enantioselective Hydrocyanation of Aldehydes 180
Contents IX
5.8 Enantioselective Mannich-Type Reactions 180
5.9 Other Enantioselective Aza-Reactions 185
5.10 Chiral Boron Receptors 187
References 188
6 Achiral Al(II1) Lewis Acids
Takashi Ooi and Keiji Maruoka 191
6.1 Introduction 191
6.2 Aluminum Halides 191
6.3 Aluminum Alkoxides 194
6.4 Alkyl Aluminums 202
6.4.1 Trialkyl Aluminums and Alkylaluminum Halides 202
6.4.2 Heteroatom-Substituted Alkylaluminums 234
6.5 Modified Organoaluminums 238
References 277
7 Chiral Aluminum Lewis Acids in Organic Synthesis
WilliamD . Wulff 283
7.1 Introduction 283
7.2 Aldol Reactions 284
7.3 Carbonyl Additions and Reductions 286
7.4 Claisen Rearrangements 292
7.5 [2 + 21 and [2 + 11 Cycloadditions 297
7.6 Diels-Alder Reactions 302
7.6.1 Aluminum Catalysts from Chiral Alcohols 302
7.6.2 Aluminum Catalysts from Chiral Diols, Sulfonamides,
and P-Hydroxysulfonamides 306
7.6.3 Aluminum Catalysts from Axially Chiral Bis-Phenols 314
7.6.4 Aluminum Catalysts from Bis-Sulfonamides 320
7.7 Ene Reactions 325
7.8 Epoxide-Opening Reactions 327
7.9 Free-Radical Reactions 329
7.10 Friedel-Crafts Reaction 333
7.11 Heteroatom Diels-Alder Reactions 334
7.12 Michael Addition Reactions 339
7.13 Strecker Reaction 350
Acknowledgment 352
References 352
8 Silicon(1V) Lewis Acids
Masataka Oishi 355
8.1 Introduction 355
8.2 Preparation of Organosilicon Lewis acids 355
8.2.1 Trimethylsilyl Triflate (la) [5c] 357
X Contents
8.2.2 Trimethylsilyl (7) [9a] 357
bis(Trifluoromethanesulfony1)imide
8.2.3 Trimethylsilyl Perchlorate (6a) [lob] 357
8.2.4 Iodotrimethylsilane [70] 357
8.2.5 Trimethylsilyl [11] 357
tetrakis(Trifluoromethanesulfony1)borate
8.3 Reactions Promoted or Catalyzed by Silicon-Based Lewis Acids 358
8.3.1 Aldol-Type Reactions, Allylation and Related Reactions 358
8.3.2 Intramolecular Aldol-Type Reaction and Allylation 366
8.3.3 Ring Construction 368
8.3.4 Isomerization and rearrangement 374
8.3.5 Glycosidation 378
8.3.6 Reduction and Oxidation 380
8.4 Reactions via Hypervalent Silicon Species 382
8.5 Conclusions 389
References 389
9 Sn(I1) and Sn(1V) Lewis Acids
Kazuaki Zshihara 395
9.1 Introduction 395
9.2 SnX2-Catalyzed Reactions 396
9.2.1 Sn(I1) Halide-Catalyzed Reactions 396
9.2.2 Sn(OTf)2-Catalyzed Reactions 400
9.3 SnX4-Catalyzed Reactions 408
9.3.1 SnC14-CatalyzedR eactions 408
9.3.2 SnC14-ZnC12-Catalyzed Reactions 427
9.3.3 Carbornetalation Reactions of Organotin Compounds
Generated Using SnC14-Bu3N 429
9.3.4 SnC14-BH (Bronsted Acid)-catalyzed Reactions 430
9.4 Organotin(1V)-catalyzed Reactions 443
9.4.1 Esterification 443
9.4.2 Transformation to Carbamate 444
9.4.3 Preparation of Cyclic Thioacetals 444
9.4.4 Chemoselective Michael and Aldol Reactions 445
9.4.5 Allylation 447
References 448
10 Preparation and Lewis-Acid-Promoted Addition Reactions
of Allylic and Allenic Tin and Indium Reagents
James A. Marshall 453
10.1 Introduction 453
10.2 Toxicity 454
10.3 Preparation of Allylic Trialkylstannanes 455
10.4 Additions of Trialkyl Allylic Stannanes to Aldehydes and Ketones 456
10.5 Lewis Acid Catalysis of Allyltin Additions 466
10.6 Catalysis by Chiral Lewis Acids 470
10.7 Additions that Proceed by Transmetalation 474
10.8 Additions of Allylic Halostannanes to Aldehydes 479
Contents XI
10.9 Additions of Achiral and Racemic Oxygenated Allylic Stannanes
to Aldehydes 480
10.10 Enantioenriched Oxygenated Allylic Stannanes 484
10.10.1 a-Oxygenated Allylic Stannanes 484
10.10.2 y-Oxygenated Allylic Stannanes 487
10.11 Reactions with Chiral a-Oxygenated Aldehydes 491
10.12 Transmetalations of Chiral Oxygenated Allylic Stannanes 495
10.12.1 SnC14 495
10.12.2 InC13 499
10.12.3 Intramolecular Reactions 503
10.13 Preparation of Allenylstannanes 507
10.14 Addition of Allenyl and Propargyl Stannanes to Aldehydes 509
10.15 Intramolecular Additions 514
10.16 Transmetalations 514
10.16.1 SnC14 514
10.16.2 InC13 518
10.17 Concluding Remarks 520
Acknowledgments 520
References 520
Volume 2
11 Sb(II1) and Sb(V) Lewis Acids
Kazuaki Ishihara 523
11.1 Introduction 523
11.2 SbX3-Catalyzed Reactions 523
11.3 SbX5-Catalyzed Reactions 525
11.3.1 Friedel-Crafts and Related Chemistry 525
11.3.2 Isomerization and Rearrangements 528
11.3.3 Other Reactions 529
11.4 HX-SbF5-Catalyzed Reactions 530
11.4.1 Generation of Stable Carbocations 530
11.4.2 Friedel-Crafts and Related Chemistry 531
11.4.3 Isomerization and Rearrangements 532
11.4.4 Cyclization 533
11.4.5 Formation of Aromatic Sulfoxides 534
11.4.6 Formylation and Carboxylation 534
11.4.7 Oxyfunctionalization of Hydrocarbons 535
11.4.8 Other Reactions 537
References 538
12 Copper Lewis Acids in Organic Synthesis
Mukund F! Sihi and Gregory R. Cook 543
12.1 Introduction 543
12.2 Dehydration 544