Catalytic C-C bond cleavage and C-Si bond formation in the reaction of RCN with Et3SiH promoted by an iron complex
Catalytic C-C bond cleavage of acetonitrile and C-Si bond formation have been attained in the photoreaction of MeCN with Et3SiH in the presence of an iron complex, Cp(CO)2FeMe. This catalytic system can be applied for arylnitrile C-C
Nakazawa, Hiroshi,Kamata, Kouji,Itazaki, Masumi
p. 4004 - 4006
(2007/10/03)
Trimethylsilyl Cyanide - A Reagent for Umpolung, V. Nucleophilic Acylation of Alkylating Reagents with α,β-Unsaturated Aldehydes.
The readily accessible adducts 3 from α,β-unsaturated aldehydes and trimethylsilyl cyanide react smoothly after deprotonation (LDA) as anions 3A with different alkylating agents in 1-position.Removal of the protective group under mild conditions yields the α,β-unsaturated ketones 5 in 60 - 80 percent overall yield.The stability of anions 3A is increased by an O-triethylsilyl group.Alkylation of 3A in 3-position (partly) is caused by 3-acceptor substituents.Nucleophilic acylation with α-alkoxyaldehydes produces 1,2-diketones via a new route.