Inner Mongolia Key Laboratory of Fine Organic Synthesis College of Chemistry and Chemical Engineering, Inner Mongolia University, 235 Daxue West Rd, Hohhot, 010021, P. R. China.
College of Chemistry and Chemical Engineering, Xinjiang Agricultural University, Urumqi, 830052, P. R. China.
Chem Asian J. 2023 Jun 1;18(11):e202300160. doi: 10.1002/asia.202300160. Epub 2023 Apr 27.
New methods for preparation of chiral alkyl fluorides have been studied intensively in recent years due to the favorable physicochemical and biological properties of those structures. Herein, we describe the regio- and enantioselective allylic alkylation of α-pyridyl-α-fluoroesters with allyl acetates promoted by Cu/Pd synergistic catalysis, constructing the carbon- fluorine quaternary stereocenters. In this co-catalytic system, palladium catalyst mainly constructed the C-C bond, while chiral copper catalyst controlled the enantioselectivity. A series of aryl- and aliphatic-substituted allyl acetates are applied, giving the corresponding products in high yield, excellent enantioselectivity, and E/Z (up to 98% yield, 98 : 2 er, E/Z>20 : 1).
近年来，由于手性烷基氟化物具有有利的物理化学和生物性质，因此人们对手性烷基氟化物的制备方法进行了深入研究。在此，我们描述了在 Cu/Pd 协同催化作用下，通过α-吡啶-α-氟代酯与烯丙基乙酸酯的区域和对映选择性烯丙基烷基化反应，构建了碳-氟季立体中心。在这个共催化体系中，钯催化剂主要构建了 C-C 键，而手性铜催化剂控制了对映选择性。一系列芳基和脂肪取代的烯丙基乙酸酯被应用，以高收率、优异的对映选择性和 E/Z（高达 98%的收率，98 : 2 er，E/Z>20 : 1）得到相应的产物。
