Synthesis of Carbon-Phosphorus Bonds, Second Edition

Cover......Page 1
Synthesis of Carbon-Phosphorus Bonds, Second Edition......Page 3
ISBN-13: 9780849316173......Page 4
Preface to the Second Edition......Page 5
Preface to the First Edition......Page 6
Table of Contents......Page 7
The Authors......Page 15
Abstract......Page 17
1.1 Recent advances in C–P bond formation......Page 18
1.2 Nomenclature of C–P compounds......Page 20
1.3 Information sources for C–P compounds......Page 22
Methoden der Organischen Chemie, Vol. 12 (Parts 1 and 2)......Page 23
Topics in Phosphorus Chemistry, Vols. 1–11......Page 24
2.1 Introduction......Page 25
2.2.1 White phosphorus......Page 26
2.2.3 Black phosphorus......Page 27
2.3 Attack on elemental phosphorus by nucleophiles......Page 28
2.5 Direct addition to \nπ\n-systems......Page 33
2.6 Oxidative additions with olefins......Page 35
2.7.1 Preparation of tris(2-carbamoylethyl)phosphine oxide — Preparation of a tertiary phosphine oxide from white phosphorus under aqueous basic conditions......Page 36
2.7.4 Preparation of benzylphosphonic acid — Preparation of a phosphonic acid from red phosphorus in aqueous acid......Page 37
References......Page 38
3.2.1 General......Page 42
3.2.2 Mechanism......Page 44
3.2.3.1 Trialkyl phosphites, dialkyl alkylphosphonites, and alkyl dialkylphosphinites......Page 45
3.2.3.3 Silyl esters of phosphorous, phosphonous, and phosphinous acids......Page 48
3.2.4 Recent advances......Page 49
3.3.2 Mechanism......Page 51
3.3.3 Reagents......Page 52
3.3.4 Recent advances......Page 53
3.4.2 Neutral trivalent phosphorus addition to unsaturated carbon......Page 56
3.4.3 Anionic trivalent phosphorus addition to unsaturated carbon......Page 59
3.4.4 Recent advances......Page 61
3.5.1 General......Page 63
3.5.2 Neutral phosphorus reagents in conjugate additions......Page 64
3.5.3 Anionic phosphorus reagents in conjugate additions......Page 66
3.5.4 Recent advances in addition to conjugated and unconjugated olefinic sites......Page 67
3.6.1 Preparation of trisodium phosphonoformate — Reaction of a chloroformate with a trialkyl phosphite and cleavage of the ester linkages......Page 70
3.6.3 Preparation of 2,3-dioleoyloxypropylphosphonic acid — Reaction of an alkyl halide with a silyl phosphite ester......Page 71
3.6.6 Preparation of triethyl 2-phosphonobutanoate — Reaction of a trialkyl phosphite with a 2-halocarboxylate ester......Page 72
3.6.8 Preparation of diphenyl benzyloxycarbonylaminomethanephosphonate — Reaction of a triaryl phosphite with an N-acetoxymethylcarbamate generated in situ......Page 73
3.6.12 Preparation of 1-ethoxybenzylphosphonate — Reaction of a trialkyl phosphite with an acetal in the presence of boron trifluoride......Page 74
3.6.14 Preparation of diethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate — Reaction of a benzylic acetate with a trialkyl phosphite......Page 75
3.6.16 Preparation of bis-(2,2-dimethyltrimethylene)yl [(2,5-dimethyl-1,4-phenylene)dimethylene] diphosphonate — Reaction of the sodium salt of a cyclic phosphite diester with a bis-benzylic halide......Page 76
3.6.18 Preparation of [1-(diethoxyphosphinyl)ethoxy]dimethylsilane — Reaction of an aldehyde with a trialkyl phosphite in the presence of a silyl halide......Page 77
3.6.20 Preparation of 1-aminoethane-1,1-diphosphonic acid — Reaction of phosphorous acid with a nitrile......Page 78
3.6.23 Preparation of diethyl 1-(trimethylsiloxy)octylphosphonate — Reaction of a mixed silyl–alkyl phosphite with an aldehyde......Page 79
3.6.26 Preparation of 1-aminobutyl-1,4-diphosphonic acid — Reaction of an aldehyde with a triaryl phosphite in the presence of a thiourea......Page 80
3.6.28 Preparation of ethyl methyl(2-carbomethoxy-3-phenylpropyl)phosphinate — Addition of a monobasic phosphinous ester to an unsaturated ester in the presence of a silylating agent......Page 81
3.6.30 Preparation of 3-diethoxyphosphinyl-2-methylpropionamide — Addition of a monobasic trivalent phosphorus acid to an unsaturated amide in the presence of an alkoxide base......Page 82
3.6.32 Preparation of phenyl(mesitylyl)(b-cyanoethyl)phosphine — Addition of a secondary phosphine to an unsaturated nitrile under aqueous basic conditions......Page 83
References......Page 84
4.2.1 General......Page 112
4.2.2 Generation of the phosphorus–halogen linkage......Page 113
4.3.2.1 Organomercury reagents......Page 117
4.3.2.3 Grignard reagents......Page 118
4.3.2.4 Aluminum-based systems......Page 120
4.3.2.5 Organocadmium reagents......Page 121
4.3.2.7 Lithium reagents......Page 122
4.3.2.8 Enamines......Page 125
4.4 Addition reactions of P–H compounds......Page 126
4.5 Addition reactions of P–Cl compounds......Page 128
4.6 Rearrangements resulting in the formation of new P–C bonds......Page 130
4.7.1 Preparation of diallyl phosphorochloridate — Preparation of a dialkyl phosphorochloridate from a dialkyl phosphite by the Todd reaction......Page 133
4.7.4 Preparation of diethyl 3-trifluoromethylphenylphosphonate — Reaction of a Grignard reagent with a dialkyl phosphorochloridate......Page 134
4.7.6 Preparation of n-butyldichlorophosphine — Monoalkylation of phosphorus trichloride using an organocadmium reagent......Page 135
4.7.8 Preparation of bis(4-methoxyphenyl)phenylphosphine oxide — Reaction of a Grignard reagent with a phosphorus halide......Page 136
4.7.10 Preparation of 2-[1,3]dithianyldiphenylphosphine oxide — Reaction of a chlorophosphine with a stabilized carbanion reagent......Page 137
4.7.11 Preparation of 2,5-dimethylbenzenephosphinic acid — Aluminum chloride-mediated reaction of phosphorus trichloride with an aromatic hydrocarbon......Page 138
4.7.14 Preparation of propadienylphosphonic dichloride — Rearrangement of a propargylic trivalent phosphorus ester......Page 139
4.7.17 Preparation of diethyl 1-(4-pyridyl)-1,2-dihydropyridine-2-phosphonate — Reaction of phosphorus trichloride with a pyridylpyridinium chloride......Page 140
References......Page 141
5.2 General structure of pentacoordinate phosphorus......Page 152
5.3.2 Stereochemistry......Page 153
5.3.3 Syntheses......Page 156
5.4.1 General......Page 157
5.4.2 Carbon–phosphorus bond-forming reactions......Page 158
5.5.1 Preparation of tetra(p-methoxymethyl) phenylphosphonium bromide — Preparation of a tetraarylphosphonium salt precursor to a pentaarylphosphorane......Page 161
5.5.4 Preparation of 2,2,2-triethoxy-2,2-dihydro-5-methyl-1,2l5-oxaphospholene — Preparation of an oxyphosphorane by reaction of a trialkyl phosphite with an a,b -unsaturated carbonyl compound......Page 162
References......Page 163
6.2.1 Approaches reminiscent of reactions in aliphatic series......Page 167
6.2.2 Transition metal-assisted reactions......Page 171
6.2.3 Friedel–Crafts-type reactions......Page 173
6.2.5 Other approaches......Page 174
6.3.1 Transition metal-assisted reactions......Page 175
6.3.2 Uncatalyzed replacement of vinylic halogen......Page 176
6.3.3 Miscellaneous reactions......Page 177
6.4.2 Preparation of dimethyl 2-methylphenylphosphonate — Photoinduced reaction of an aryl iodide with a trialkyl phosphite......Page 180
6.4.5 Preparation of dimethyl pyridin-4-ylphosphonate — Reaction of an N -pyridonepyridinium salt with a trialkyl phosphite......Page 181
6.4.8 Preparation of diisopropyl 2,2-diphenylvinylphosphonate — Reaction of a vinyl bromide with a Cu(I) complex of a trialkyl phosphite......Page 182
References......Page 183