Synthesis of Carbon-Phosphorus Bonds, Second Edition

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ISBN: 9780849316173 | 0849316170
Cover: Hardcover
Copyright: 12/18/2003

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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 syntheses ñ along with the new approaches towards the preparation of compounds with aromatic and vinylic C-P bonds. Detailed surveys of IUPAC nomenclature recommendations, common notation systems, and various experimental examples help to make the book an effective source of critical and annotated references for organic and phosphorus chemists specifically, or for any chemists working with C-P bonds.

Chapter 1 Introduction

(8)

1.1 Recent advances in C-P bond formation

(2)

1.2 Nomenclature of C-P compounds

(2)

1.3 Information sources for C-P compounds

(4)

Chapter 2 Synthesis of organophosphorus compounds from elemental phosphorus

(18)

2.1 Introduction

(1)

2.2 Availability of elemental phosphorus

(2)

2.2.1 White phosphorus

(1)

2.2.2 Red phosphorus

(1)

2.2.3 Black phosphorus

(1)

2.2.4 General reactivity

(1)

2.3 Attack on elemental phosphorus by nucleophiles

(5)

2.4 Radical attack on elemental phosphorus

(1)

2.5 Direct addition to π-systems

(2)

2.6 Oxidative additions with olefins

(1)

2.7 Experimental procedures

(2)

2.7.1 Preparation of tris(2-carbamoylethyl)phosphine oxide - Preparation of a tertiary phosphine oxide from white phosphorus under aqueous basic conditions

(1)

2.7.2 Preparation of phenylphosphine - Preparation of a primary phosphine from white phosphorus with an organometallic

(1)

2.7.3 Preparation of α-hydroxy-p-methylbenzylphosphonous acid - Preparation of a phosphonous acid from red phosphorus in aqueous medium

(1)

2.7.4 Preparation of benzylphosphonic acid - Preparation of a phosphonic acid from red phosphorus in aqueous acid

(1)

2.8 Summary

(1)

References

(5)

Chapter 3 C-P bond formation using nucleophilic trivalent phosphorus reagents

(70)

3.1 Introduction

(1)

3.2 Substitution reactions using neutral trivalent phosphorus reagents

(9)

3.2.1 General

(2)

3.2.2 Mechanism

(1)

3.2.3 Reagents

(4)

3.2.3.1 Trialkyl phosphites, dialkyl alkylphosphonites, and alkyl dialkylphosphinites

(3)

3.2.3.2 Triaryl phosphites, diaryl alkylphosphonites, and aryl dialkylphosphinites

(1)

3.2.3.3 Silyl esters of phosphorous, phosphonous, and phosphinous acids

(1)

3.2.4 Recent advances

(2)

3.3 Substitution reactions using anionic trivalent phosphorus reagents

(5)

3.3.1 General

(1)

3.3.2 Mechanism

(1)

3.3.3 Reagents

(1)

3.3.4 Recent advances

(3)

3.4 Preparations of α-substituted phosphoryl compounds

(7)

3.4.1 General

(1)

3.4.2 Neutral trivalent phosphorus addition to unsaturated carbon

(3)

3.4.3 Anionic trivalent phosphorus addition to unsaturated carbon

(2)

3.4.4 Recent advances

(2)

3.5 Conjugate addition reactions

(7)

3.5.1 General

(1)

3.5.2 Neutral phosphorus reagents in conjugate additions

(2)

3.5.3 Anionic phosphorus reagents in conjugate additions

(1)

3.5.4 Recent advances in addition to conjugated and unconjugated olefinic sites

(3)

3.6 Experimental procedures 55

3.6.1 Preparation of trisodium phosphonoformate - Reaction of a chloroformate with a trialkyl phosphite and cleavage of the ester linkages

(1)

3.6.2 Preparation of tris(trimethylsilyl) phosphite - Preparation of a silyl ester of a trivalent phosphorus acid for Michaelis-Arbuzov reaction

(1)

3.6.3 Preparation of 2,3-dioleoyloxypropylphosphonic acid - Reaction of an alkyl halide with a silyl phosphite ester

(1)

3.6.4 Preparation of dimethyl (4-methoxybenzyl)phosphonate - Reaction of a benzyl halide with a trialkyl phosphite

(1)

3.6.5 Preparation of 5-(3-benzoylpropionyl)-3-deoxy-3 diisopropoxyphosphinylmethyl-1,2-di-0-acetyl-D ribofuranose - Reaction of an alkyl bromide in a carbohydrate series with triisopropyl phosphite

(1)

3.6.6 Preparation of triethyl 2-phosphonobutanoate - Reaction of a trialkyl phosphite with a 2-halocarboxylate ester

(1)

3.6.7 Preparation of 1-isopropoxy-2-methylpropylphosphonate - Reaction of a trialkyl phosphite with a 1-chloroether

(1)

3.6.8 Preparation of diphenyl benzyloxycarbonylaminomethanephosphonate - Reaction of a triaryl phosphite with an N-acetoxymethylcarbamate generated in situ

(1)

3.6.9 Preparation of diethyl isobutyrylphosphonate - Reaction of a trialkyl phosphite with a carboxylic acid chloride

(1)

3.6.10 Preparation of (diethyl phosphonomethyl) acetyl sulfide - Reaction of a trialkyl phosphite with a 1-halosulfide

(1)

3.6.11 Preparation of diethyl 1-oxo-2-(3-indolyl)ethanephosphonate - Reaction of a trialkyl phosphite with a carboxylic acid chloride in solution

(1)

3.6.12 Preparation of 1-ethoxybenzylphosphonate - Reaction of a trialkyl phosphite with an acetal in the presence of boron trifluoride

(1)

3.6.13 Preparation of 1,10-diphenyl-1,10-diphosphacyclooctadecane 1,10-dioxide - Reaction of an alkyl halide with a phosphinite ester generated in situ by reduction of a phosphinate

(1)

3.6.14 Preparation of diethyl 3,5-di-t-butyl-4hydroxybenzylphosphonate - Reaction of a benzylic acetate with a trialkyl phosphite

(1)

3.6.15 Preparation of diethyl 3,3-diethoxypropynyl-1-phosphonate - Reaction of a sodium salt of a dialkyl phosphite with an acetylenic halide

(1)

3.6.16 Preparation of bis-(2,2-dimethyltrimethylene)yl [(2,5dimethyl-1,4-phenylene)dimethylene] diphosphonate - Reaction of the sodium salt of a cyclic phosphite diester with a bis-benzylic halide

(1)

3.6.17 Preparation of di-n-butyl N,Ndiethylcarbamoylmethylphosphonate - Phase transfer-catalyzed reaction of a dialkyl phosphite with an alkyl chloride

(1)

3.6.18 Preparation of [1-(diethoxyphosphinyl)ethoxy]dimethylsilane - Reaction of an aldehyde with a trialkyl phosphite in the presence of a silyl halide

(1)

3.6.19 Preparation of 0, 0-diphenyl 2-methylthio-1-(N phenylthioureido)ethylphosphonate - Reaction of tiphenyl phosphite with an imide generated in situ in the presence of acetic acid

(1)

3.6.20 Preparation of 1-aminoethane-1,1-diphosphonic acid - Reaction of phosphorous acid with a nitrile

(1)

3.6.21 Preparation of N-benzyl a-aminobenzylphosphonic acid - Reaction of phosphorous acid with an imine

(1)

3.6.22 Preparation of benzyliminodimethylenediphosphonic acid - Reaction of phosphorous acid with a formaldimine generated in situ

(1)

3.6.23 Preparation of diethyl 1-(trimethylsiloxy)octylphosphonate - Reaction of a mixed silyl-alkyl phosphite with an aldehyde....

(1)

3.6.24 Preparation of (SP)-t-butyl(phenyl)(α-hydroxybenzyl) phosphine oxide - Reaction of a chiral secondary phosphine with an aldehyde under basic conditions

(1)

3.6.25 Preparation of diethyl (S)-cc-hydroxybenzylphosphonate - Reaction of an aldehyde with a dialkyl phosphite facilitated by a chiral BINOL complex

(1)

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

(1)

3.6.27 Preparation of diphenyl 1-(benzylcarbamoyl)-4(phthalimido)-1-phosphonate - Reaction of a phthalimidoprotected aminoaldehyde with a triaryl phosphite in the presence of benzyl carbamate

(1)

3.6.28 Preparation of ethyl methyl(2-carbomethoxy-3phenylpropyl)phosphinate - Addition of a monobasic phosphinous ester to an unsaturated ester in the presence of a silylating agent

(1)

3.6.29 Preparation of 2-dimethoxyphosphinyl-2-methoxy-2phenylacetaldehyde oxime - Reaction of an unsaturated nitro compound with a trialkyl phosphite in the presence of an alcohol

(1)

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

(1)

3.6.31 Preparation of di-n-butyl di-n-butoxyphosphinylsuccinate - Addition of a monobasic trivalent phosphorus reagent to an unsaturated ester in the presence of base

(1)

3.6.32 Preparation of phenyl(mesitylyl)(β-cyanoethyl)phosphine - Addition of a secondary phosphine to an unsaturated nitrile under aqueous basic conditions

(1)

3.6.33 Preparation of 1-ethoxy-2-phenyl-4,5-dimethoxycarbonyl Δ2-λphospholene 1-oxide - Reaction of a vinylicphosphonite diester with an unsaturated carboxylate ester

(1)

3.6.34 Preparation of phenyl (β-carbomethoxyethyl) phosphine-borane - Reaction of a primary phosphineborane with an unsaturated ester

(1)

References

(28)

Chapter 4 C-P bond formation via displacement, addition, or rearrangement

(40)

4.1 Introduction

(1)

4.2 Phosphorus-halogen compounds

(5)

4.2.1 General

(1)

4.2.2 Generation of the phosphorus-halogen linkage

(4)

4.3 Substitution reactions on phosphorus-halogen compounds using organometallics and related reagents

102

(9)

4.3.1 General

102

(1)

4.3.2 Types of organometallic reagents

102

(16)

4.3.2.1 Organomercury reagents

102

(1)

4.3.2.2 Organolead compounds

103

(1)

4.3.2.3 Grignard reagents

103

(2)

4.3.2.4 Aluminum-based systems

105

(1)

4.3.2.5 Organocadmium reagents

106

(1)

4.3.2.6 Organotin reagents

107

(1)

4.3.2.7 Lithium reagents

107

(3)

4.3.2.8 Enamines

110

(1)

4.4 Addition reactions of P-H compounds

111

(2)

4.5 Addition reactions of P-Cl compounds

113

(2)

4.6 Rearrangements resulting in the formation of new P-C bonds

115

(3)

4.7 Experimental procedures

118

(8)

4.7.1 Preparation of diallyl phosphorochloridate - Preparation of a dialkyl phosphorochloridate from a dialkyl phosphite by the Todd reaction

118

(1)

4.7.2 Preparation of 2-chloromethyl-2-ethyl-1,3-propanediol phosphorochloridate - Preparation of a dialkyl phosphorochloridate by reaction of a trialkyl phosphite with chlorine

119

(1)

4.7.3 Preparation of isopropyl methylphosphonochloridate - Preparation of a phosphonochloridate by reaction of a phosphonate diester with phosgene

119

(1)

4.7.4 Preparation of diethyl 3-trifluoromethylphenylphosphonate - Reaction of a Grignard reagent with a dialkyl phosphorochloridate

119

(1)

4.7.5 Preparation of vinyldichlorophosphine - Reaction of phosphorus trichloride with an organomercury compound

120

(1)

4.7.6 Preparation of n-butyldichlorophosphine - Monoalkylation of phosphorus trichloride using an organocadmium reagent

120

(1)

4.7.7 Preparation of diethyl 3-diphenylthiophosphoryl-2morpholino-1-cyclohexenylphosphonous acid - Reaction of an enamine with a phosphorus halide and subsequent esterification

121

(1)

4.7.8 Preparation of bis(4-methoxyphenyl)phenylphosphine oxide - Reaction of a Grignard reagent with a phosphorus halide

121

(1)

4.7.9 Preparation of diethyl 1-hydroxy-2-butynephosphonate - Reaction of a phosphorus halide with a 2-alkynol and subsequent rearrangement to generate a hydroxyphosphonate

122

(1)

4.7.10 Preparation of 2-[1,3]dithianyldiphenylphosphine oxide - Reaction of a chlorophosphine with a stabilized carbanion reagent

122

(1)

4.7.11 Preparation of 2,5-dimethylbenzenephosphiníc acid - Aluminum chloride-mediated reaction of phosphorus trichloride with an aromatic hydrocarbon

123

(1)

4.7.12 Preparation of (1-aminopropyl)phenylphosphinic acid - Reaction of a carbonyl compound with benzyl carbamate and a dichlorophosphine

124

(1)

4.7.13 Preparation of diethyl 5-methoxytetrahydrofuran-2ylphosphonate - Reaction of an acetal with a phosphorochloridite

124

(1)

4.7.14 Preparation of propadienylphosphonic dichloride - Rearrangement of a propargylic trivalent phosphorus ester

124

(1)

4.7.15 Preparation of 2-chlorohept-1-ylphosphonic dichloride - Reaction of an alkene with phosphorus pentachloride

125

(1)

4.7.16 Preparation of 6-amino-1-hydroxyhexylidenediphosphonic acid - Reaction of a carboxylic acid with phosphorous acid and phosphorus trichloride

125

(1)

4.7.17 Preparation of diethyl 1-(4-pyridyl)-1,2-dihydropyridine2-phosphonate - Reaction of phosphorus trichloride with a pyridylpyridinium chloride

125

(1)

References

126

(11)

Chapter 5 Pentacoordinate phosphorus

137

(16)

5.1 Introduction

137

(1)

5.2 General structure of pentacoordinate phosphorus

137

(1)

5.3 Stable phosphoranes

138

(4)

5.3.1 General

138

(1)

5.3.2 Stereochemistry

138

(3)

5.3.3 Syntheses

141

(1)

5.4 Carbon-phosphorus bond formation involving phosphorane intermediates

142

(4)

5.4.1 General

142

(1)

5.4.2 Carbon-phosphorus bond-forming reactions

143

(3)

5.5 Experimental procedures

146

(2)

5.5.1 Preparation of tetra(p-methoxymethyl) phenylphosphonium bromide - Preparation of a tetraarylphosphonium salt precursor to a pentaarylphosphorane

146

(1)

5.5.2 Preparation of pentaphenylphosphorane - Preparation of a phosphorane from a phosphonium salt and an organolithium reagent

147

(1)

5.5.3 Preparation of 2,2,2-trimethoxy-3-phenyl-4-acetyl-5methyl-Δ-oxaphospholene - Preparation of an oxyphosphorane by reaction of a trialkyl phosphite with an α,β-unsaturated carbonyl compound

147

(1)

5.5.4 Preparation of 2,2,2-triethoxy-2,2-dihydro-5-methyl-1,2X5oxaphospholene -Preparation of an oxyphosphorane by reaction of a trialkyl phosphite with an α,β-unsaturated carbonyl compound

147

(1)

5.5.5 Preparation of diethyl [(2R*)-2-{1(S*)-hydroxyphenyl}-3oxobutyl] phosphonate - Preparation of a functionalized phosphonate by reaction of an oxaphospholene with an aldehyde

148

(1)

References

148

(5)

Chapter 6 Aromatic and vinylic C-P bonds

153

(22)

6.1 Introduction

153

(1)

6.2 Aromatic carbon-phosphorus bond formation

153

(8)

6.2.1 Approaches reminiscent of reactions in aliphatic series

153

(4)

6.2.2 Transition metal-assisted reactions

157

(2)

6.2.3 Friedel-Crafts-type reactions

159

(1)

6.2.4 Use of organometallics

160

(1)

6.2.5 Other approaches

160

(1)

6.3 Vinylic carbon-phosphorus bond formation

161

(5)

6.3.1 Transition metal-assisted reactions

161

(1)

6.3.2 Uncatalyzed replacement of vinylic halogen

162

(1)

6.3.3 Miscellaneous reactions

163

(3)

6.4 Experimental procedures

166

(3)

6.4.1 Preparation of diethyl phenylphosphonate - Reaction of an aryl halide with a dialkyl phosphite in the presence of a Pd(0) catalyst and a tertiary amine

166

(1)

6.4.2 Preparation of dimethyl 2-methylphenylphosphonate - Photoinduced reaction of an aryl iodide with a trialkyl phosphite

166

(1)

6.4.3 Preparation of 4-methoxyphenylphosphonous dichloride - Friedel-Crafts reaction of a substituted benzene with phosphorus trichloride

167

(1)

6.4.4 Preparation of diethyl 4-acetylphenylphosphonate - Reaction of an acyl halide with a trialkyl phosphite catalyzed by Ni(II)

167

(1)

6.4.5 Preparation of dimethyl pyridin-4-ylphosphonate - Reaction of an N-pyridonepyridinium salt with a trialkyl phosphite

167

(1)

6.4.6 Preparation of diethyl pyridine-2-phosphonate - Reaction of an N-methoxy pyridinium salt with a dialkyl phosphite salt

168

(1)

6.4.7 Preparation of diethyl (Z)-1-propenylphosphonate - Reaction of a vinylic bromide with a dialkyl phosphite catalyzed by Pd(0)

168

(1)

6.4.8 Preparation of diisopropy12,2-diphenylvinylphosphonate - Reaction of a vinyl bromide with a Cu(I) complex of a trialkyl phosphite

169

(1)

6.4.9 Preparation of diisopropyl (E)-2-benzoylvinylphosphonate - Reaction of a trialkyl phosphite with a β-halovinyl ketone

169

(1)

References

169

(6)

Index

175

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Synthesis of Carbon-Phosphorus Bonds, Second Edition

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