A Reactivity Switch in the Gold-Catalysed Coupling of Allyl Sulfides with Propargylic Carboxylates

Abstract

The gold-catalysed coupling of allyl sulfides with propargylic carboxylates follows different pathways depending upon the choice of nonmigrating group on the sulfur and the aromatic group at the propargylic position of the alkyne substrate.

Key words

gold - sulfur ylides - alkynes - propargylic carboxylates - coupling

References and Notes

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7

We observed cyclopropanation as the major pathway when allyl sulfides bearing greater substitution at the alkene were employed.

12

Only very limited success has been observed with aliphatic substituents at the propargylic position. Aldehyde-derived systems are observed to give only trace amounts of con-
version or undergo degradation. Ketone derivative A-1 proceeds sluggishly to give the desired coupling product
A-3a in low yield (Scheme  [6] ).

Scheme 6

14

Similarly, neither (E)- or (Z)-6gd were observed when 3gd was added to an ongoing reaction.