Silicon Reagents for Organic Synthesis

ISBN-13: 9783642686634 / Angielski / Miękka / 2011 / 430 str.

William P. Weber

Opis

The application of silicon reagents in organic synthesis has grown at an increasingly rapid rate over the last twenty years. This has been the result of truly international interest. Signifi- cant contributions have been made by Japanese, Russian, Ger- man, French, English, American, Swiss and Canadian as well as by chemists from many other countries. This monograph attempts to comprehensively cover this field. Some seventeen hundred articles reporting contributions by over eighteen hundred scientists are summarized. Nevertheless, I have no doubt that interesting and important work has been left out. I welcome comments about such results which should be in- cluded in any future editions of this monograph. I would like to thank Robert Damrauer who first stimulated my interest in organosilicon chemistry. In addition, I thank a number of chemists who have shared my enthusiasm for silicon chemistry over the years: A Chihi, M.E. Childs, R.A Felix, H. Firgo, T.Y. Gu, T.Llto, LN. Jung, K.E. Koenig, H.Okinoshima, M.M. Radcliffe, B.L Rosen, H.S.D. Soy sa, K.P. Steele, R.E. Swaim, D. Tzeng, P.B. Valkovich, AK. Will- ard, S. Wunderly, and present members of my research group.

Spis treści

1 Fundamental Considerations.- 2 Chemistry of Trimethylsilyl Cyanide.- 2.1 Introduction.- 2.2 Addition of Trimethylsilyl Cyanide to Polar Multiple Bonds.- 2.3 Utility of Trimethylsilyl Ethers of Cyanohydrins.- 2.4 Acyl Substitution Reactions of Trimethylsilyl Cyanide.- 2.5 Reactions of Trimethylsilyl Cyanide with Polar Cumulenes.- 2.6 Substitution Reactions of Trimethylsilyl Cyanide.- 2.7 Synthesis of Trimethylsilyl Cyanide.- 3 Trimethylsilyl Iodide and Bromide.- 3.1 Introduction.- 3.2 Cleavage of Ethers.- 3.3 Cleavage of Acetals and Ketals.- 3.4 Conversion of Alcohols and Alkoxytrimethylsilanes to Alkyl Iodides.- 3.5 Reaction of TMS-Br with Alcohols.- 3.6 Reaction of Oxiranes with TMS-I—Conversion to Allylic Alcohols.- 3.7 Hydrolysis of Esters.- 3.8 Hydrolysis of Carbamates.- 3.9 Hydrolysis of Dialkyl Phosphonates.- 3.10 Preparation of ?-and ?-Iodo Ketones.- 3.11 Preparation of TMS-Br and TMS-I.- 4 Silyl Azides.- 4.1 Introduction.- 4.2 Preparation and Properties of Organosilyl Azides.- 4.3 Cycloaddition Reactions.- 4.4 Reactions with Aldehydes or Ketones.- 4.5 Reactions with Epoxides.- 4.6 Reactions with Cumulenes.- 4.7 Reactions with Phosphines.- 4.8 Reactions with Grignard Reagents.- 4.9 Reactions with Acid Chlorides or Anhydrides.- 4.10 Reactions with Lead Tetraacetate or Phenyliodosodiacetate.- 5 Silyl Nitronates.- 5.1 Introduction-Physical and Spectroscopic Properties.- 5.2 Cycloaddition Reactions.- 5.3 Nitro-Aldol Reactions.- 5.4 Oxidation.- 5.5 Preparation.- 6 Peterson Reaction.- 6.1 Introduction.- 6.2 ?-Silyl Organometallics.- A. ?-Silyl Grignard and Organolithium Reagents.- B. Halogen-Metal Exchange.- C. Addition of Organometallics to Vinyl Silanes.- D. Metallation.- E. Displacement Reactions.- 6.3 Stereochemical Control of Elimination.- 6.4 Preparation of Substituted Alkenes.- A. Ketene Thioacetals.- B. Vinyl Sulfoxides.- C. Thio Enol Ethers.- D. Sulfines.- E. Allenes.- F. Vinyl Silanes.- G. Vinyl Boronic Esters.- H. Cross Aldol Reaction-?,?-Unsaturated Aldehydes.- I. ?,?-Unsaturated Carboxylic Acids.- J. ?,?-Unsaturated Nitriles.- K. ?,?-Unsaturated Esters.- L. ?-Ylidene-?-butyrolactones.- M. Silyl Reformatsky Reaction.- N. ?,?-Unsaturated Thiol Esters.- O. ?,?-Unsaturated Amides.- P. Imines.- 6.5 Related Reactions.- 7 Vinyl Silanes.- 7.1 Introduction.- 7.2 Elimination of Trimethylhalosilanes from ?-Halosilanes.- 7.3 Stereospecificity of Elimination.- 7.4 Electrophilic Substitution Reactions.- A. Halogens.- B. Reactions of ?-Trimethylsilyl Epoxides with Electrophiles.- C. ?-Sily1 Styrenes.- D. Protodesilylation of Vinyl Silanes.- E. Friedel-Crafts Acylation Reactions.- F. Friedel-Crafts Alkylation.- G. Sulfenyl Halides.- H. Palladium Chloride.- 7.5 Addition of Carbanions to Vinyl Silanes.- 7.6 Masked Carbonyl Groups.- 7.7 1,2-Transposition of Carbonyl Groups.- 7.8 Cycloaddition Reactions.- 7.9 Preparation of Vinyl Silanes.- A. E-1-Trimethylsilyl-1-alkenes.- B. Z-1-Trimethylsilyl-1-alkenes.- C. 2-Trimethylsilyl-1-alkenes.- D. 1-Cycloalkenyltrimethylsilanes.- E. E- and Z-1,2-Dialkyl-l-trimethylsilyl ethylenes.- F. 1,2-Disub stituted- 1,2- bis(trimethylsilyl)ethylene, 1,1-Di substituted-2,2-bis(trimethylsilyl)ethylenes and 1,1,2-Trisubstituted-2-trimethylsilyl ethylenes.- 8 Aryl Silanes.- 8.1 Introduction.- 8.2 Protodesilylation.- 8.3 Halodesilylation.- 8.4 Metallo-desilylation.- 8.5 Sulfo-desilylation.- 8.6 Acyl-desilylation.- 8.7 Alkyl-desilylation.- 8.8 Diazo-desilylation.- 8.9 Nitrodesilylation.- 8.10 Aryl Silanes as Organometallic Reagents.- 8.11 Preparation.- 9 Silyl Acetylenes.- 9.1 Introduction.- 9.2 Addition Reactions.- 9.3 Electrophilic Substitution.- A. Protic Acids.- B. Halogens.- C. Acyl Chlorides.- D. Sulfonyl Chlorides-Sulfur Trioxide.- E. Aldehydes and Ketones.- F. Carbocations.- 9.4 Protection of Terminal Alkynes.- 9.5 Cycloaddition Reactions.- A. Diels-Alder Reactions.- B. Silyl-ynamines.- C. Cobalt-Catalyzed Cycloadditions.- D. [2 + 2] and [2 + 3] Cycloadditions.- 9.6 Preparation of Silylacetylenes.- A. 1-Trialkylsilylalkynes.- B. 1-Trialkylsilyl-2-alkynes.- C. 1-Trialkylsilyl-1,2-dienes.- D. 1-Trimethylsilyl-2,3-dienes.- 10 Tetraalkylsilanes, Alkylpentafluorosilicates and Alkenylpentafluorosilicates.- 10.1 Introduction.- 10.2 Electrophilic Cleavage of Tetraalkylsilanes.- A. Protic Acids.- B. Acylium Ions.- C. Carbocations.- D. Halogens.- E. Trimethylsilyl Chlorosulfonate.- 10.3 Preparation.- 10.4 Alkylpentafluorosilicates.- 10.5 Reaction of Alkylpentafluorosilicates with Halogens.- 10.6 Reaction with m-Chloroperbenzoic Acid.- 10.7 Reaction with TCNE.- 10.8 Reduction.- 10.9 Exchange.- 10.10 Alkenylpentafluorosilicates.- 10.11 Electrophilic Cleavage of Alkenylpentafluorosilicates.- 11 Allylic Silanes.- 11.1 Introduction.- 11.2 Electrophilic Substitution.- A. Protic Acids.- B. Halogens.- C. Acid Chlorides.- D. Sulfonyl Chlorides.- E. Transition Metal Complexes.- F. Sulfenyl Halides.- G. Carbocations.- H. Ketones, Aldehydes, Acetals, and Ketals.- I. ?,?-Unsaturated Ketones and Aldehydes.- J. ?-Nitro Alkenes.- K. ?-and ?-Keto Acetals and ?-Keto Esters.- 11.3 Cycloaddition Reactions of Allylic Silanes.- A. [2 + 2] Cycloaddition Reactions.- B. [3 + 2] Cycloaddition Reactions.- C. Diels-Alder Reactions.- 11.4 Preparation.- A. Direct Synthesis.- B. Catalytic Reactions of Disilanes.- C. Pyrolysis.- D. Hydrosilation Reactions.- E. Dissolving Metal Reductions.- F. Wittig Reactions.- G. Allylic Organometallics.- 11.5 Silyl Substituted Allylic Anions.- 11.6 Boron Substituted Allylic Silanes.- 12 Electrophilic Reactions of Silyl Enol Ethers.- 12.1 Introduction.- 12.2 Carbocations.- 12.3 ?-Methylene Ketones.- 12.4 Cationic Iron Tricarbonyl Complexes.- 12.5 Halogens.- 12.6 ?-Halo Acyl Silanes.- 12.7 Pseudo Halogens, Sulfenyl and Selenyl Halides.- 12.8 Nitrosonium and Nitronium Cations.- 12.9 Mercuric Salts.- 12.10 Acid Chlorides.- 12.11 Aldehydes and Ketones.- 12.12 Silyl-Reformatsky Reactions.- 12.13 Acetals and Ketals.- 12.14 ?,?-Unsaturated Ketones, Ketals and Acetals.- 12.15 ?-Nitro Alkenes.- 12.16 Relative Reactivities.- 12.17 Hydroboration.- 13 Oxidation of Silyl Enol Ethers.- 13.1 Introduction.- 13.2 Preparation of ?,?-Unsaturated Ketones.- 13.3 Preparation of 1,4-Diketones.- 13.4 Preparation of ?-Acyloxy and a-Hydroxy Ketones.- 13.5 Baeyer-Villiger Oxidation of ?-Trimethylsilyloxy Ketones.- 13.6 Ozonolysis of Silyl Enol Ethers.- 13.7 Reaction of Singlet Oxygen with Silyl Enol Ethers.- 14 Cyclopropanation of Silyl Enol Ethers, Chemistry of Trimethylsilyloxycyclopropanes.- 14.1 Introduction.- 14.2 Preparation of Trimethylsilyloxycyclopropanes. Regiospecific Conversion to Methyl Ketones.- 14.3 Acid Catalyzed Rearrangement of 1-Vinyl-1-trimethylsilyloxycyclopropanes.- 14.4 Pyrolysis of 1-Vinyl-1-trimethylsilyloxycyclopropanes.- 14.5 Reactions of Electrophiles with Trimethylsilyloxycyclopropanes.- 14.6 Reactions of Silyl Enol Ethers with Other Carbenes.- 15 Cycloaddition and Electrocyclic Reactions of Silyl Enol Ethers.- 15.1 Introduction.- 15.2 [2 + 2] Cycloaddition Reactions.- 15.3 Diels-Alder, [4 + 2] Cycloaddition Reactions.- 15.4 [3 + 4] and [3 + 2] Cycloaddition Reactions.- 15.5 Electrocyclic Reactions of Silyl Enol Ethers.- 16 Preparation of Silyl Enol Ethers.- 16.1 Introduction.- 16.2 Rearrangement of ?-Sily1 Ketones.- 16.3 Brook Rearrangement, ?-Silyl Ketones.- 16.4 Preparation of ?-Silyl Ketones.- 16.5 Conjugate Addition/Generation of Specific Lithium Enolates from Silyl Enol Ethers.- 16.6 Hydrosilation of Ketones.- 16.7 Silyl-Hydroformylation Reactions.- 16.8 1,4-Hydrosilation of ?,?-Unsaturated Carbonyl Compounds.- 16.9 Catalytic Isomerization of Allyloxyltrimethylsilanes.- 16.10 Dissolving Metal Reduction.- 16.11 Non-Nucleophilic Bases.- 16.12 TMS-Cl/Triethylamine/DMF and Related Systems.- 17 Ionic Hydrogenations.- 17.1 Introduction.- 17.2 Ionic Hydrogenation of Alkenes-Reduction of Carbocations.- 17.3 Stability of Functional Groups to Ionic Hydrogenation.- 17.4 Ionic Hydrogenation-Reduction of Non-Classical Carbocations.- 17.5 Ionic Hydrogenation of Sigma Bonds.- 17.6 Reduction of Ketones.- 17.7 Reduction of Aldehydes.- 17.8 Reduction of N-Alkyl Nitrilium and N-Acyliminium Salts.- 17.9 Reduction of ?,?-Unsaturated Ketones.- 17.10 Reduction of Heteroaromatic Nuclei-Thiophenes.- 17.11 Reduction of Organometallic Complexes.- 17.12 Improved Procedures.- 18 Reduction of Polar Multiple Bonds of Hydrosilation.- 18.1 Introduction.- 18.2 Hydrosilation of Ketones and Aldehydes.- 18.3 Catalytic Asymmetric Hydrosilation of Aldehydes and Ketones.- 18.4 Asymmetric Hydrosilation of a-Keto Esters.- 18.5 Hydrosilation of Imines and Pyridines.- 18.6 Hydrosilation of Isocyanates and Carbodiimides.- 18.7 Silyl-Rosenmund Reduction.- 19 Dissolving Metal Reductions.- 19.1 Introduction.- 19.2 Ketones and Aldehydes.- 19.3 ?,?-Unsaturated Ketones and Aldehydes.- 19.4 Esters/Silyl-Acyloin Reactions.- 19.5 ?,?-Unsaturated Esters, Amides, and Acid Chlorides.- 19.6 Amides.- 19.7 ?,?-Unsaturated Nitriles.- 19.8 1,3-Dienes.- 19.9 Acetylenes.- 19.10 Styrenes.- 19.11 Aromatics-Silyl Birch Reduction.- 19.12 Allylic and Benzylic Ethers.- 19.13 Epoxides.- 19.14 Carbon-Sulfur Bonds.- 19.15 ?-Nitroalkenes and Oximes.- 20 Miscellaneous Reductions.- 20.1 Introduction.- 20.2 Tin-Hydride Mediated Reductions.- 20.3 Silyl Radicals.- A. Reduction of Alkyl Halides.- B. Reduction of Chloroformates.- C. Reduction of Acyl Fluorides.- D. Reduction of Esters and Lactones.- 20.4 Reduction with Trichlorosilane and Tertiary Amines.- 20.5 Reduction of Phosphine Oxides.- A. Trichlorosilane-tertiary amines/hexachlorodisilane.- B. Phenylsilane.- 20.6 Reduction of Sulfoxides.- 20.7 Reduction of Amine Oxides.- 20.8 Reduction of ?-Halo Ketones.- 21 Silicon-Sulfur.- 21.1 Introduction.- 21.2 Epoxides and Oxetanes.- 21.3 Aldehydes and Ketones.- 21.4 Esters.- 21.5 Cumulenes.- 21.6 Allylic Acetals and Benzylic Acetates.- 21.7 Silyl-Pummerer Rearrangements.- A. Synthesis of Aldehydes.- B. Synthesis of Ketones.- C. Preparation of 1-Phenylthioalkyltrimethylsilanes.- D. Synthesis of Aldehydes/Selenium-Silicon Reagents.- E. Synthesis of a,ß-Unsaturated Aldehydes.- 21.8 Exchange Reactions.- A. Synthesis of Sulfides.- B. Synthesis of Polysulfides.- C. Synthesis of S-alkyl Thiocarboxylates.- D. Sulfur Transfer Reagents.- 21.9 Miscellaneous.- 21.10 Preparation.- 22 Silicon-Phosphorous.- 22.1 Introduction.- 22.2 Alkyl Halides-Arbuzov Reactions.- 22.3 Acid Chlorides.- A. Acyl Phosphonates.- B. Acyl Phosphates.- C. Acyl Phosphines.- 22.4 Ketones and Aldehydes.- 22.5 Benzoquinones.- 22.6 ?-Keto Esters and ?-Keto Nitriles.- 22.7 ?,?-Unsaturated Carbonyl Compounds.- 22.8 ?-Haloketones.- 22.9 Carbon-Carbon Bond Formation/Acyl Anion Synthons.- 22.10 Oxidation of Trimethylsilyl Phosphites.- 22.11 Miscellaneous Reactions.- 22.12 Preparations.- 23 Silyl Oxidants.- 23.1 Introduction.- 23.2 bis(Trimethylsilyl) monoperoxysulfate.- 23.3 bis(Trimethylsilyl)peroxide and t-Butyltrimethylsilyl peroxide.- 23.4 Silyl Hydroperoxides.- 23.5 Silyl Chromate.- 23.6 bis(Silyl) Bromamine.- 23.7 Silica Gel Mediated Oxidations.- 24 Silyl Bases.- 24.1 Introduction.- 24.2 Lithium 1,1-bis(trimethylsilyl) Alkoxides.- 24.3 Alkali bis(trimethylsilyl) Amides.- A. Ketone Enolate Anions.- B. Ester Enolate Anions.- C. Cyano-Stabilized Anions.- D. Ylids.- E. Carbenes.- 25 Silicon-Fluorine.- 25.1 Introduction.- 25.2 Generation of Carbanions and Enolate Anions.- 25.3 Generation of Carbenes. a-Elimination.- 25.4 1,2-, 1,4- and 1,6-Elimination Reactions.- Author Index.