Phosphonamide Stabilized Allylic Carbanions. New Homoenolate Anion Equivalents

David A. Evans, James M. Takacs, Kenneth M. Hurst

Research output: Contribution to journalArticle

108 Citations (Scopus)

Abstract

The chemistry of phosphonamide stabilized allylic carbanions derived from the 1,2-addition of tervalent phosphorus siloxanes with α,β-unsaturated aldehydes has been studied. An in situ synthesis of allylic α-silyloxyphosphonamides, followed by metalation and regioselective γ-alkylation of the allylic carbanion, yields a versatile “active ester”. Transesterification under mild conditions gives esters and lactones and defines a new homoenolate equivalency.

Original languageEnglish (US)
Pages (from-to)371-378
Number of pages8
JournalJournal of the American Chemical Society
Volume101
Issue number2
DOIs
StatePublished - Feb 1 1979

Fingerprint

Anions
Esters
Negative ions
Siloxanes
Transesterification
Alkylation
Lactones
Aldehydes
Phosphorus

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Phosphonamide Stabilized Allylic Carbanions. New Homoenolate Anion Equivalents. / Evans, David A.; Takacs, James M.; Hurst, Kenneth M.

In: Journal of the American Chemical Society, Vol. 101, No. 2, 01.02.1979, p. 371-378.

Research output: Contribution to journalArticle

@article{7b11d2f6c56f4781a0b06b070fa6af96,
title = "Phosphonamide Stabilized Allylic Carbanions. New Homoenolate Anion Equivalents",
abstract = "The chemistry of phosphonamide stabilized allylic carbanions derived from the 1,2-addition of tervalent phosphorus siloxanes with α,β-unsaturated aldehydes has been studied. An in situ synthesis of allylic α-silyloxyphosphonamides, followed by metalation and regioselective γ-alkylation of the allylic carbanion, yields a versatile “active ester”. Transesterification under mild conditions gives esters and lactones and defines a new homoenolate equivalency.",
author = "Evans, {David A.} and Takacs, {James M.} and Hurst, {Kenneth M.}",
year = "1979",
month = "2",
day = "1",
doi = "10.1021/ja00496a016",
language = "English (US)",
volume = "101",
pages = "371--378",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Phosphonamide Stabilized Allylic Carbanions. New Homoenolate Anion Equivalents

AU - Evans, David A.

AU - Takacs, James M.

AU - Hurst, Kenneth M.

PY - 1979/2/1

Y1 - 1979/2/1

N2 - The chemistry of phosphonamide stabilized allylic carbanions derived from the 1,2-addition of tervalent phosphorus siloxanes with α,β-unsaturated aldehydes has been studied. An in situ synthesis of allylic α-silyloxyphosphonamides, followed by metalation and regioselective γ-alkylation of the allylic carbanion, yields a versatile “active ester”. Transesterification under mild conditions gives esters and lactones and defines a new homoenolate equivalency.

AB - The chemistry of phosphonamide stabilized allylic carbanions derived from the 1,2-addition of tervalent phosphorus siloxanes with α,β-unsaturated aldehydes has been studied. An in situ synthesis of allylic α-silyloxyphosphonamides, followed by metalation and regioselective γ-alkylation of the allylic carbanion, yields a versatile “active ester”. Transesterification under mild conditions gives esters and lactones and defines a new homoenolate equivalency.

UR - http://www.scopus.com/inward/record.url?scp=0000605665&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000605665&partnerID=8YFLogxK

U2 - 10.1021/ja00496a016

DO - 10.1021/ja00496a016

M3 - Article

AN - SCOPUS:0000605665

VL - 101

SP - 371

EP - 378

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 2

ER -