Episulfone substitution and ring-opening reactions via alpha-sulfonyl carbanion intermediates

A P  Dishington; R E  Douthwaite; A  Mortlock; A B  Muccioli; N S  Simpkins

Episulfone substitution and ring-opening reactions via alpha-sulfonyl carbanion intermediates

A P Dishington, R E Douthwaite, A Mortlock, A B Muccioli, N S Simpkins

Chemistry

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

Abstract

Three-membered cyclic sulfones undergo substitution on treatment with base-electrophile mixtures, such as LDA-Me(3)SiCl and Bu(t)-P-4 phosphazene base-PhCHO, to give either substituted episulfones or the corresponding alkenes following loss of SO2. The structure of a trisilylated episulfone product, 2a, was determined by X-ray crystallography. In the absence of Me(3)SiCl, reaction of episulfones with lithium diisopropylamide results in ring-opening to give alkenyl sulfinate intermediates, which can be alkylated to give (E)-alkenyl sulfone products in stereoselective fashion.

Original language	English
Pages (from-to)	323-337
Number of pages	15
Journal	Journal of the Chemical Society-Perkin Transactions 1
Issue number	3
Publication status	Published - 7 Feb 1997

Keywords

SECONDARY REACTIONS
TERTIARY-AMINES
LITHIUM
ANIONS
VINYLSILANES
CHLORIDES
STEREOCHEMISTRY
S,N-ADDUCTS
ACETYLENES
MECHANISM

Cite this

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title = "Episulfone substitution and ring-opening reactions via alpha-sulfonyl carbanion intermediates",

abstract = "Three-membered cyclic sulfones undergo substitution on treatment with base-electrophile mixtures, such as LDA-Me(3)SiCl and Bu(t)-P-4 phosphazene base-PhCHO, to give either substituted episulfones or the corresponding alkenes following loss of SO2. The structure of a trisilylated episulfone product, 2a, was determined by X-ray crystallography. In the absence of Me(3)SiCl, reaction of episulfones with lithium diisopropylamide results in ring-opening to give alkenyl sulfinate intermediates, which can be alkylated to give (E)-alkenyl sulfone products in stereoselective fashion.",

keywords = "SECONDARY REACTIONS, TERTIARY-AMINES, LITHIUM, ANIONS, VINYLSILANES, CHLORIDES, STEREOCHEMISTRY, S,N-ADDUCTS, ACETYLENES, MECHANISM",

author = "Dishington, {A P} and Douthwaite, {R E} and A Mortlock and Muccioli, {A B} and Simpkins, {N S}",

year = "1997",

month = feb,

day = "7",

language = "English",

pages = "323--337",

journal = "Journal of the Chemical Society-Perkin Transactions 1",

issn = "0300-922X",

publisher = "Chemical Society",

number = "3",

}

TY - JOUR

T1 - Episulfone substitution and ring-opening reactions via alpha-sulfonyl carbanion intermediates

AU - Dishington, A P

AU - Douthwaite, R E

AU - Mortlock, A

AU - Muccioli, A B

AU - Simpkins, N S

PY - 1997/2/7

Y1 - 1997/2/7

N2 - Three-membered cyclic sulfones undergo substitution on treatment with base-electrophile mixtures, such as LDA-Me(3)SiCl and Bu(t)-P-4 phosphazene base-PhCHO, to give either substituted episulfones or the corresponding alkenes following loss of SO2. The structure of a trisilylated episulfone product, 2a, was determined by X-ray crystallography. In the absence of Me(3)SiCl, reaction of episulfones with lithium diisopropylamide results in ring-opening to give alkenyl sulfinate intermediates, which can be alkylated to give (E)-alkenyl sulfone products in stereoselective fashion.

AB - Three-membered cyclic sulfones undergo substitution on treatment with base-electrophile mixtures, such as LDA-Me(3)SiCl and Bu(t)-P-4 phosphazene base-PhCHO, to give either substituted episulfones or the corresponding alkenes following loss of SO2. The structure of a trisilylated episulfone product, 2a, was determined by X-ray crystallography. In the absence of Me(3)SiCl, reaction of episulfones with lithium diisopropylamide results in ring-opening to give alkenyl sulfinate intermediates, which can be alkylated to give (E)-alkenyl sulfone products in stereoselective fashion.

KW - SECONDARY REACTIONS

KW - TERTIARY-AMINES

KW - LITHIUM

KW - ANIONS

KW - VINYLSILANES

KW - CHLORIDES

KW - STEREOCHEMISTRY

KW - S,N-ADDUCTS

KW - ACETYLENES

KW - MECHANISM

M3 - Article

SN - 0300-922X

SP - 323

EP - 337

JO - Journal of the Chemical Society-Perkin Transactions 1

JF - Journal of the Chemical Society-Perkin Transactions 1

IS - 3

ER -