Shi Xiaonan, Li Sida, Wu Lipeng
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, 730000, P. R. China.
Angew Chem Int Ed Engl. 2019 Nov 4;58(45):16167-16171. doi: 10.1002/anie.201908931. Epub 2019 Sep 30.
The first example of an efficient and direct dehydrogenative boration of alkenes for vinyl boronate ester synthesis was achieved using a zirconium catalyst. Our methodology avoids using precious transition metals, additional hydrogen acceptors, high temperatures, and long reaction times, which were required to overcome the reducing ability of borane, to give alkyl boronate esters. Detailed mechanistic studies revealed a reversible reaction pathway and further suggested applying the zirconium complex as a "shuttle catalyst" for transfer boration, which thus sidesteps the use of relatively sensitive borane.
使用锆催化剂实现了用于合成乙烯基硼酸酯的烯烃高效直接脱氢硼化的首个实例。我们的方法避免了使用贵金属过渡金属、额外的氢受体、高温以及长反应时间，而这些是生成烷基硼酸酯时克服硼烷还原能力所必需的。详细的机理研究揭示了一条可逆反应途径，并进一步表明将锆配合物用作转移硼化的“穿梭催化剂”，从而避免了使用相对敏感的硼烷。
