Controllable Single and Double Difluoromethylene Insertions into C–Cu Bonds: Copper-Mediated Tetrafluoroethylation and Hexafluoropropylation of Aryl Iodides with TMSCF<sub>2</sub>H and TMSCF<sub>2</sub>Br
作者:Xiu Wang、Shitao Pan、Qinyu Luo、Qian Wang、Chuanfa Ni、Jinbo Hu
DOI:10.1021/jacs.2c03104
日期:2022.7.13
The selective difluoromethylene insertion into a C–Cu bond is a challenging task and is currently limited to either a single CF2 insertion into CuCF3 or double CF2 insertions into CuC6F5 (or (Z)-CF3CF = CFCu). Achieving both selective single and double CF2 insertions into the same C–Cu bond is even more difficult. Herein, highly controllable single and double CF2 insertions into CuCF2H species with
选择性地将二氟亚甲基插入 C-Cu 键是一项具有挑战性的任务,目前仅限于单 CF 2插入 CuCF 3或双 CF 2插入 CuC 6 F 5(或 ( Z )-CF 3 CF = CFCu) . 在相同的 C-Cu 键中实现选择性单和双 CF 2插入甚至更加困难。在此,已经描述了使用 TMSCF 2 Br 试剂将高度可控的单和双 CF 2插入到 CuCF 2 H 物质中,提供了两种以前未知的氟烷基铜物质“Cu(CF 2 ) nCF 2 H” ( n = 1 和 2) 在不同反应条件下独立。这项工作代表了单和双 CF 2以高选择性方式插入同一 C-Cu 键的第一个例子。所获得的“Cu(CF 2 ) n CF 2 H” ( n = 1 和 2) 物质的合成价值通过它们与芳基碘、卤化剂和肉桂酰氯的反应来证明,这使得 HCF 2 CF的直接转移成为可能2和HCF 2 CF 2 CF 2部分变成有机分子。碳氟化合物链可控伸长率的关键1到