A copper(I)-catalyzed enantioselective addition of enynes to ketones was developed. The method allows facile construction of enantiomerically enriched tertiary alcohols using skipped enynes as stable hydrocarbon pronucleophiles. The combination of a soft copper(I)-conjugated Brønsted base catalyst with a chiral diphosphine ligand, (S,S)-Ph-BPE, enabled chemoselective deprotonation of the skipped enynes in the presence of ketones bearing intrinsically more acidic α-protons. The catalytically generated chiral allylcopper species enantio-, diastereo-, regio-, and chemoselectively reacted with ketones, thereby demonstrating excellent substrate generality with functional group tolerance. The skipped enyne moieties of the pronucleophiles were exclusively converted to cis-conjugated enynes, which will eventually allow for further versatile transformations.

中文翻译：

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铜（I）催化的烯炔与酮的对映选择性加成

开发了铜（I）催化的烯炔与酮的对映选择性加成。该方法允许使用跳过的烯炔作为稳定的烃亲核试剂轻松构建对映异构体富集的叔醇。软铜 (I)-共轭 Brønsted 碱催化剂与手性二膦配体 (S,S)-Ph-BPE 的组合，能够在带有本质上更具酸性的 α-质子的酮的存在下对跳过的烯炔进行化学选择性去质子化。催化生成的手性烯丙基铜物种对映-、非对映-、区域-和化学选择性与酮反应，从而表现出优异的底物通用性和官能团耐受性。亲核试剂的跳过的烯炔部分专门转化为顺式共轭烯炔，