A. Ricci et al., REGIOSELECTIVE AND STEREOSELECTIVE METAL-MEDIATED SYNTHESIS OF POLYFUNCTIONALIZED ALKENES, Pure and applied chemistry, 68(3), 1996, pp. 679-682
Silyl- and stannylcupration of alkynes bearing N- or S-based functiona
l groups takes place in a regio- and stereoselective fashion and the r
esulting vinyl metal species are easily quenched with a wide range of
electrophiles, thereby resulting in a flexible and general route to po
lysubstituted silylated or stannylated olefins. For the replacement of
the vinylic R(3)M framework in the allylic-type systems Pd(0) catalys
is is needed and through Stille-type (M=Sn) or Heck-type (M=Si) reacti
ons, the controlling factors on the regio- and stereochemistry of the
synthesis of di- and trisubstituted olefins are disclosed, Conversely
displacement of the R(3)Si group and functionalization with electrophi
les at C-2 can be performed even in the absence of catalysts when N or
S atoms are directly bound to the C=C moiety as part of enamino or vi
nylsulfide frameworks respectively.