Catalytic Enantioselective Synthesis of Allylic Boronates Bearing a Trisubstituted Alkenyl Fluoride and Related Derivatives
Catalytic Enantioselective Synthesis of Allylic Boronates Bearing a Trisubstituted Alkenyl Fluoride and Related Derivatives
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DOI：
10.1002/anie.201906283
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发表时间：
2019-07-16
影响因子：
16.6
通讯作者：
Ito, Hajime
中科院分区：
文献类型：
--
作者：
Akiyama, Sota;Kubota, Koji;Ito, Hajime
公开了第一种非对映和对映选择性合成带有Z-三取代烯基氟的烯丙基硼酸酯的催化方法。用Z-或E-烯丙基二氟化物进行硼基取代，并由双膦/Cu络合物催化，以高达99%的产率提供产物，具有>98：2的Z/E选择性和99：1的对映体比。各种随后的修饰是可行的，值得注意的例子是非对映选择性地添加到醛/醛亚胺，以获得含有氟取代的立体季中心的高烯丙醇/胺。
The first catalytic method for diastereo- and enantioselective synthesis of allylic boronates bearing a Z-trisubstituted alkenyl fluoride is disclosed. Boryl substitution is performed with either a Z- or E-allyldifluoride and is catalyzed by bisphosphine/Cu complexes, affording products in up to 99 % yield with >98:2 Z/E selectivity and 99:1 enantiomeric ratio. A variety of subsequent modifications are feasible, and notable examples are diastereoselective additions to aldehydes/aldimines to access homoallylic alcohols/amines containing a fluorosubstituted stereogenic quaternary center.