The unprecedented copper-catalyzed asymmetric alkynylallylic monofluoroalkylation reaction is described via the use of 1,3-enynes and fluorinated malonates. A series of 1,4-enynes bearing a monofluoroalkyl unit are achieved in high yields, excellent regio- and enantioselectivity and high E/Z selectivity. The asymmetric propargylic monofluoroalkylation is also developed. The reliability and synthetic value of the work are highlighted by a gram-scale test and a couple of downstream transformations. Preliminary mechanistic studies unveil a negative nonlinear effect for the catalytic process.

中文翻译：

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不对称铜催化氟化丙二酸酯的炔烯丙基单氟烷基化

通过使用 1,3-烯炔和氟化丙二酸酯描述了前所未有的铜催化不对称炔基烯丙基单氟烷基化反应。一系列带有单氟烷基单元的 1,4-烯炔以高收率、优异的区域选择性和对映选择性以及高E/Z选择性获得。不对称炔丙基单氟烷基化也得到了发展。克级测试和一些下游转化凸显了这项工作的可靠性和综合价值。初步机理研究揭示了催化过程的负面非线性效应。