碳 nucleophiles 的催化潜力很少向碳 electrophiles 由于他们的反应被揭示了形成稳定的碳碳契约它太强壮,不能为期望的催化周期被劈开。我们开发了羰基混合物的有效催化 cyanosilylation 与一在里面 situ 产生了链烯 / 磷化氢当它的 nucleophilicity 被翻译成催化活动时,使内收,它被调节不在反应条件下面结合羰基混合物或电子缺乏的链烯。面对甲基 acrylate 的 3 mol% 和 triphenylphosphine,大量烷基, alkenyl,和芳基的 3 mol% ,酉同类和醛在房间温度与 trimethylsilyl 氰化物经历 cyanosilylation 反应产出在结构上在优秀收益的多样化的氰醇 silyl 醚。由为羰基混合物的 cyanosilylation 把甲基 acrylate/triphenylphosphine 用作一个高度有效的亲核的催化剂系统,这研究证明为利用链烯 / 磷化氢的 nucleophilicity 的有用 organocatalysis 的发展的一个新概念使内收在 situ 产生了。
The catalytic potential of carbon nucleophiles has seldom been disclosed due to their reactivity toward carbon electrophiles to form stable carbon-carbon bonds, which are too strong to be cleaved for the expected catalytic cycles. We have developed an efficient catalytic cyanosilylation of carbonyl compounds with an in situ generated alkene/phosphine adduct, which is tuned not to couple with a carbonyl compound or an electron-deficient alkene under the reaction conditions when its nucleophilicity is trans- lated into catalytic activity. In the presence of 3 mol% of methyl acrylate and 3 mol% of triphenylphosphine, a broad range of alkyl, alkenyl, and aryl ketones and aldehydes undergo cyanosilylation reaction with trimethylsilyl cyanide at room temperature to yield structurally diversified cyanohydrin silyl ethers in excellent yields. By using methyl acrylate/triphenylphosphine as a highly effective nucleophilic catalyst system for the cyanosilylation of carbonyl compounds, this study demonstrates a new concept for the development of useful organocatalysis utilizing the nucleophilicity of alkene/phosphine adducts generated in situ.