Department of Chemistry, Faculty of Science , Hokkaido University , Sapporo 060-0810 , Japan.
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD) , Hokkaido University , Sapporo 001-0021 , Japan.
J Am Chem Soc. 2019 May 1;141(17):6817-6821. doi: 10.1021/jacs.9b01952. Epub 2019 Apr 18.
Herein, we show the highly enantioselective borylation of unactivated methylene C(sp)-H bonds in 2-alkylpyridines and 2-alkyl-1,3-azole derivatives using an iridium-BINOL-based chiral monophosphite catalyst system. Quantum chemical calculations using the artificial force induced reaction (AFIR) method suggested that a monophosphite-Ir-tris(boryl) complex generates a narrow chiral reaction pocket where the differentiation of the enantiotopic methylene C-H bonds is accomplished through an assembly of multiple noncovalent interactions.
在此，我们展示了使用基于铱-BINOL 的手性单膦配体催化剂体系，对 2-烷基吡啶和 2-烷基-1,3-唑衍生物中的未活化亚甲基 C(sp)-H 键进行高对映选择性硼化反应。使用人工力诱导反应 (AFIR) 方法的量子化学计算表明，单膦配体-铱-三硼基配合物生成了一个狭窄的手性反应口袋，其中通过多种非共价相互作用的组装完成对映异位亚甲基 C-H 键的区分。
