Copper-catalyzed allylic difluoromethylation of allyl carbonates with (difluoromethyl)zinc reagent
Copper-catalyzed allylic difluoromethylation of allyl carbonates with (difluoromethyl)zinc reagent
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DOI：
10.1016/j.jfluchem.2017.07.018
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发表时间：
2017-11-01
影响因子：
1.9
通讯作者：
Mikami, Koichi
中科院分区：
文献类型：
--
作者：
Aikawa, Kohsuke;Ishii, Koki;Mikami, Koichi
以二氟碘甲烷和二乙基锌的碘-锌交换反应制备了二氟甲基锌试剂，并以铜盐为催化剂，实现了碳酸烯丙酯的烯丙基二氟甲基化反应。二氟甲基化反应不仅产率高，而且具有完全的区域选择性。此外，该反应被证明是立体特异性的，因此手性烯丙基二氟甲基化的化合物可以通过处理手性底物来获得，所述手性底物通过催化不对称氢化α，β-不饱和羰基化合物来合成。
The catalytic allylic difluoromethylation of allyl carbonates with (difluoromethyl)zinc reagent, which can be readily prepared via iodine-zinc exchange reaction of difluoroiodomethane with diethylzinc, was achieved by employing copper salt as a catalyst. The difluoromethylation proceeded with not only good-to-high yields but also complete regioselectivity. Furthermore, the reaction was demonstrated to be stereospecific, and hence chiral allylic difluoromethylated compound can be obtained by treatment of chiral substrates which are synthesized through catalytic asymmetric hydrogenation of alpha,beta-unsaturated carbonyl compounds.