1606174-97-3Relevant academic research and scientific papers
Regioselective 1,4- over 1,2-addition of 3,3-bis(silyl) allyloxy lithium to enals, enones and enoates. the remarkable α-effect of silicon
Ye, Xincui,Sun, Xianwei,Huang, Zhenggang,Yang, Na,Su, Zhishan,Hu, Changwei,Song, Zhenlei
, p. 3021 - 3025 (2014)
A remarkable α-effect of silicon has been discovered that results in soft nucleophilicity at the Cγ of 3,3-bis(silyl) allyloxy lithium 1. The addition of 1 to α,β-unsaturated carbonyl compounds, including enals, proceeds in a 1,4- over 1,2-manner with medium to good regioselectivity, whereas the parent allyloxy lithium 4 undergoes complete 1,2-addition. The results from DFT calculations of HMPA-complexed 1 and 4 provide the rationale to explain this different regioselectivity.
