Silylformylations stereospecific

This tandem intramolecular silylformylation/Sakurai reaction has successfully been applied in a formal total synthesis of mycoticin A [75]. The scope and utility of these reactions was expanded to (Z)- and (E)-crotyl groups leading to the stereospecific incorporation of both anti and syn propionate units into the growing polyol chain (Scheme 21) [76]. 

The development of the first alkyne silylformylation reaction was reported in 1989 by Matsuda [27]. Alkynes were treated with Me2PhSiH and Et3N with 1 mol% Rh4(CO)i2 under CO pressure to produce yS-silyl-a,/ -unsaturated aldehydes (Scheme 5.20). A second report from Ojima detailed the development of rhodium-cobalt mixed metal clusters as effective catalysts for alkyne silylformylation [28]. Shortly thereafter, Doyle reported that rhodium(II) perfluorobutyrate was a highly efficient and selective catalyst for alkyne silylformylation under remarkably mild reaction conditions (0°C, 1 atm CO) [29]. In all these reports, terminal alkynes react regiospedfically with attachment of the silane to the unsubstituted end of the alkyne. The reaction is often (but not always) stereospecific, producing the cis-product preferentially. 

The reaction is regio- and stereospecific and leads to the (Z)-l-silyl-2-formyl-1-hexenes, i.e. to the silylformylation products. In the most probable catalytic cycle, the insertion of alkyne occurs into a Rh-SiR3 bond leading to an intermediate... 

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