Rhodium-Catalyzed Anti Selective Cross-Addition of Bis(trimethylsilyl)acetylene to Diarylacetylenes via Carbon-Silicon Bond Cleavage.

[摘要]：The addn. of bis(trimethylsilyl)acetylene to diarylacetylenes RCYCR (R = Ph, 4-ClC6H4, 4-MeOC6H4, 2-thienyl) proceeds efficiently and selectively in a formal anti fashion in the presence of [Rh(OH)(cod)]2/bisphosphine and phenol as catalyst and activator, resp., accompanied by cleavage of one of the C-Si bonds to produce the corresponding (Z)-enynes RCH:CRCYCSiMe3. The products can further couple with the same or a different diarylacetylene mol. to give rise to (Z,Z)-1,2,5,6-tetraaryl-1,5-hexadien-3-ynes, e.g. RCH:CRCYCCR:CHR when the same alkyne used, that show relatively strong solid-state fluorescence.

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