Synthesis of carbon-phosphorus bonds

Robert Engel0849316170, 9780849316173

Synthesis of Carbon-Phosphorus Bonds, Second Edition is a working guide for the laboratory, incorporating classical approaches with the recent developments of carbon-phosphorus (C-P) bond formation. These advances include the preparation of phosphoranes — specifically in the use of transient oxophosphoranes as intermediates in organophosphorus compound synthesis ñ along with the new approaches towards the preparation of compounds with aromatic and vinylic C-P bonds.Synthesis of Carbon-Phosphorus Bonds, Second Edition serves as a useful tool in the laboratory. It offers detailed surveys of IUPAC nomenclature recommendations, common notation systems, and various experimental examples. These features help to make this text an effective source of critical and annotated references, as well as a a working guide for organic and phosphorus chemists specifically, or for any chemists working with C-P bonds.

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Table of contents :
Synthesis of Carbon-Phosphorus Bonds, Second Edition……Page 2
Preface to the Second Edition……Page 4
Preface to the First Edition……Page 5
Table of Contents……Page 6
The Authors……Page 14
Abstract……Page 16
1.1 Recent advances in C–P bond formation……Page 17
Table of Contents……Page 0
1.2 Nomenclature of C–P compounds……Page 19
1.3 Information sources for C–P compounds……Page 21
Methoden der Organischen Chemie, Vol. 12 (Parts 1 and 2)……Page 22
Topics in Phosphorus Chemistry, Vols. 1–11……Page 23
2.1 Introduction……Page 24
2.2.1 White phosphorus……Page 25
2.2.3 Black phosphorus……Page 26
2.3 Attack on elemental phosphorus by nucleophiles……Page 27
2.5 Direct addition to
π
-systems……Page 32
2.6 Oxidative additions with olefins……Page 34
2.7.1 Preparation of tris(2-carbamoylethyl)phosphine oxide — Preparation of a tertiary phosphine oxide from white phosphorus under aqueous basic conditions……Page 35
2.7.4 Preparation of benzylphosphonic acid — Preparation of a phosphonic acid from red phosphorus in aqueous acid……Page 36
References……Page 37
3.2.1 General……Page 41
3.2.2 Mechanism……Page 43
3.2.3.1 Trialkyl phosphites, dialkyl alkylphosphonites, and alkyl dialkylphosphinites……Page 44
3.2.3.3 Silyl esters of phosphorous, phosphonous, and phosphinous acids……Page 47
3.2.4 Recent advances……Page 48
3.3.2 Mechanism……Page 50
3.3.3 Reagents……Page 51
3.3.4 Recent advances……Page 52
3.4.2 Neutral trivalent phosphorus addition to unsaturated carbon……Page 55
3.4.3 Anionic trivalent phosphorus addition to unsaturated carbon……Page 58
3.4.4 Recent advances……Page 60
3.5.1 General……Page 62
3.5.2 Neutral phosphorus reagents in conjugate additions……Page 63
3.5.3 Anionic phosphorus reagents in conjugate additions……Page 65
3.5.4 Recent advances in addition to conjugated and unconjugated olefinic sites……Page 66
3.6.1 Preparation of trisodium phosphonoformate — Reaction of a chloroformate with a trialkyl phosphite and cleavage of the ester linkages……Page 69
3.6.3 Preparation of 2,3-dioleoyloxypropylphosphonic acid — Reaction of an alkyl halide with a silyl phosphite ester……Page 70
3.6.6 Preparation of triethyl 2-phosphonobutanoate — Reaction of a trialkyl phosphite with a 2-halocarboxylate ester……Page 71
3.6.8 Preparation of diphenyl benzyloxycarbonylaminomethanephosphonate — Reaction of a triaryl phosphite with an N-acetoxymethylcarbamate generated in situ……Page 72
3.6.12 Preparation of 1-ethoxybenzylphosphonate — Reaction of a trialkyl phosphite with an acetal in the presence of boron trifluoride……Page 73
3.6.14 Preparation of diethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate — Reaction of a benzylic acetate with a trialkyl phosphite……Page 74
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 75
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 76
3.6.20 Preparation of 1-aminoethane-1,1-diphosphonic acid — Reaction of phosphorous acid with a nitrile……Page 77
3.6.23 Preparation of diethyl 1-(trimethylsiloxy)octylphosphonate — Reaction of a mixed silyl–alkyl phosphite with an aldehyde……Page 78
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 79
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 80
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 81
3.6.32 Preparation of phenyl(mesitylyl)(b-cyanoethyl)phosphine — Addition of a secondary phosphine to an unsaturated nitrile under aqueous basic conditions……Page 82
References……Page 83
4.2.1 General……Page 111
4.2.2 Generation of the phosphorus–halogen linkage……Page 112
4.3.2.1 Organomercury reagents……Page 116
4.3.2.3 Grignard reagents……Page 117
4.3.2.4 Aluminum-based systems……Page 119
4.3.2.5 Organocadmium reagents……Page 120
4.3.2.7 Lithium reagents……Page 121
4.3.2.8 Enamines……Page 124
4.4 Addition reactions of P–H compounds……Page 125
4.5 Addition reactions of P–Cl compounds……Page 127
4.6 Rearrangements resulting in the formation of new P–C bonds……Page 129
4.7.1 Preparation of diallyl phosphorochloridate — Preparation of a dialkyl phosphorochloridate from a dialkyl phosphite by the Todd reaction……Page 132
4.7.4 Preparation of diethyl 3-trifluoromethylphenylphosphonate — Reaction of a Grignard reagent with a dialkyl phosphorochloridate……Page 133
4.7.6 Preparation of n-butyldichlorophosphine — Monoalkylation of phosphorus trichloride using an organocadmium reagent……Page 134
4.7.8 Preparation of bis(4-methoxyphenyl)phenylphosphine oxide — Reaction of a Grignard reagent with a phosphorus halide……Page 135
4.7.10 Preparation of 2-[1,3]dithianyldiphenylphosphine oxide — Reaction of a chlorophosphine with a stabilized carbanion reagent……Page 136
4.7.11 Preparation of 2,5-dimethylbenzenephosphinic acid — Aluminum chloride-mediated reaction of phosphorus trichloride with an aromatic hydrocarbon……Page 137
4.7.14 Preparation of propadienylphosphonic dichloride — Rearrangement of a propargylic trivalent phosphorus ester……Page 138
4.7.17 Preparation of diethyl 1-(4-pyridyl)-1,2-dihydropyridine-2-phosphonate — Reaction of phosphorus trichloride with a pyridylpyridinium chloride……Page 139
References……Page 140
5.2 General structure of pentacoordinate phosphorus……Page 151
5.3.2 Stereochemistry……Page 152
5.3.3 Syntheses……Page 155
5.4.1 General……Page 156
5.4.2 Carbon–phosphorus bond-forming reactions……Page 157
5.5.1 Preparation of tetra(p-methoxymethyl) phenylphosphonium bromide — Preparation of a tetraarylphosphonium salt precursor to a pentaarylphosphorane……Page 160
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 161
References……Page 162
6.2.1 Approaches reminiscent of reactions in aliphatic series……Page 166
6.2.2 Transition metal-assisted reactions……Page 170
6.2.3 Friedel–Crafts-type reactions……Page 172
6.2.5 Other approaches……Page 173
6.3.1 Transition metal-assisted reactions……Page 174
6.3.2 Uncatalyzed replacement of vinylic halogen……Page 175
6.3.3 Miscellaneous reactions……Page 176
6.4.2 Preparation of dimethyl 2-methylphenylphosphonate — Photoinduced reaction of an aryl iodide with a trialkyl phosphite……Page 179
6.4.5 Preparation of dimethyl pyridin-4-ylphosphonate — Reaction of an N -pyridonepyridinium salt with a trialkyl phosphite……Page 180
6.4.8 Preparation of diisopropyl 2,2-diphenylvinylphosphonate — Reaction of a vinyl bromide with a Cu(I) complex of a trialkyl phosphite……Page 181
References……Page 182