Radical addition reactions of phosphorus hydrides: Tuning the reactivity of phosphorus hydrides, the use of microwaves and Horner-Wadsworth-Emmons-type reactions

C M  Jessop; A F  Parsons; A  Routledge; D J  Irvine

doi:10.1002/ejoc.200500907

Radical addition reactions of phosphorus hydrides: Tuning the reactivity of phosphorus hydrides, the use of microwaves and Horner-Wadsworth-Emmons-type reactions

C M Jessop, A F Parsons, A Routledge, D J Irvine

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The reactivity of phosphorus hydrides in radical addition reactions are compared, and the substituents on phosphorus are shown to affect the efficiency of the reactions. The change in reactivity is attributed to the different bond dissociation energies of the P-H bonds, which have been calculated. Phosphorus hydrides with particularly weak P-H bonds are shown to undergo radical additions by microwave irradiation, in the absence of conventional initiators. These radical addition reactions produce phosphonothioates, phosphinothioates and phosphane sulfides, which react in HWE-type reactions, to afford substituted alkenes. (c) Wiley-VCH Verlag GmbH & Co.

Original language	English
Pages (from-to)	1547-1554
Number of pages	8
Journal	European Journal of Organic Chemistry
Issue number	6
DOIs	https://doi.org/10.1002/ejoc.200500907
Publication status	Published - 13 Mar 2006

Keywords

radical reactions
heterocycles
synthetic methods
cyclisation
STEREOSELECTIVE-SYNTHESIS
HYPOPHOSPHOROUS ACID
EFFICIENT SYNTHESIS
H-PHOSPHONATE
CYCLIZATION
HYDROGEN
ESTERS
WATER
PHOSPHONOTHIOATES
REDUCTION

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10.1002/ejoc.200500907

Cite this

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title = "Radical addition reactions of phosphorus hydrides: Tuning the reactivity of phosphorus hydrides, the use of microwaves and Horner-Wadsworth-Emmons-type reactions",

abstract = "The reactivity of phosphorus hydrides in radical addition reactions are compared, and the substituents on phosphorus are shown to affect the efficiency of the reactions. The change in reactivity is attributed to the different bond dissociation energies of the P-H bonds, which have been calculated. Phosphorus hydrides with particularly weak P-H bonds are shown to undergo radical additions by microwave irradiation, in the absence of conventional initiators. These radical addition reactions produce phosphonothioates, phosphinothioates and phosphane sulfides, which react in HWE-type reactions, to afford substituted alkenes. (c) Wiley-VCH Verlag GmbH & Co.",

keywords = "radical reactions, heterocycles, synthetic methods, cyclisation, STEREOSELECTIVE-SYNTHESIS, HYPOPHOSPHOROUS ACID, EFFICIENT SYNTHESIS, H-PHOSPHONATE, CYCLIZATION, HYDROGEN, ESTERS, WATER, PHOSPHONOTHIOATES, REDUCTION",

author = "Jessop, {C M} and Parsons, {A F} and A Routledge and Irvine, {D J}",

year = "2006",

month = mar,

day = "13",

doi = "10.1002/ejoc.200500907",

language = "English",

pages = "1547--1554",

journal = "European Journal of Organic Chemistry",

issn = "1434-193X",

publisher = "Wiley-Blackwell",

number = "6",

}

TY - JOUR

T1 - Radical addition reactions of phosphorus hydrides: Tuning the reactivity of phosphorus hydrides, the use of microwaves and Horner-Wadsworth-Emmons-type reactions

AU - Jessop, C M

AU - Parsons, A F

AU - Routledge, A

AU - Irvine, D J

PY - 2006/3/13

Y1 - 2006/3/13

N2 - The reactivity of phosphorus hydrides in radical addition reactions are compared, and the substituents on phosphorus are shown to affect the efficiency of the reactions. The change in reactivity is attributed to the different bond dissociation energies of the P-H bonds, which have been calculated. Phosphorus hydrides with particularly weak P-H bonds are shown to undergo radical additions by microwave irradiation, in the absence of conventional initiators. These radical addition reactions produce phosphonothioates, phosphinothioates and phosphane sulfides, which react in HWE-type reactions, to afford substituted alkenes. (c) Wiley-VCH Verlag GmbH & Co.

AB - The reactivity of phosphorus hydrides in radical addition reactions are compared, and the substituents on phosphorus are shown to affect the efficiency of the reactions. The change in reactivity is attributed to the different bond dissociation energies of the P-H bonds, which have been calculated. Phosphorus hydrides with particularly weak P-H bonds are shown to undergo radical additions by microwave irradiation, in the absence of conventional initiators. These radical addition reactions produce phosphonothioates, phosphinothioates and phosphane sulfides, which react in HWE-type reactions, to afford substituted alkenes. (c) Wiley-VCH Verlag GmbH & Co.

KW - radical reactions

KW - heterocycles

KW - synthetic methods

KW - cyclisation

KW - STEREOSELECTIVE-SYNTHESIS

KW - HYPOPHOSPHOROUS ACID

KW - EFFICIENT SYNTHESIS

KW - H-PHOSPHONATE

KW - CYCLIZATION

KW - HYDROGEN

KW - ESTERS

KW - WATER

KW - PHOSPHONOTHIOATES

KW - REDUCTION

U2 - 10.1002/ejoc.200500907

DO - 10.1002/ejoc.200500907

M3 - Article

SP - 1547

EP - 1554

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

SN - 1434-193X

IS - 6

ER -