Wang Xianjin, Cui Xin, Li Sida, Wang Yue, Xia Chungu, Jiao Haijun, 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.
University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Angew Chem Int Ed Engl. 2020 Aug 3;59(32):13608-13612. doi: 10.1002/anie.202002642. Epub 2020 May 27.
A general and atom-economical synthesis of 1,1-diborylalkanes from alkenes and a borane without the need for an additional H acceptor is reported for the first time. The key to our success is the use of an earth-abundant zirconium-based catalyst, which allows a balance of self-contradictory reactivities (dehydrogenative boration and hydroboration) to be achieved. Our method avoids using an excess amount of another alkene as an H acceptor, which was required in other reported systems. Furthermore, substrates such as simple long-chain aliphatic alkenes that did not react before also underwent 1,1-diboration in our system. Significantly, the unprecedented 1,1-diboration of internal alkenes enabled the preparation of 1,1-diborylalkanes.
首次报道了一种从烯烃和硼烷出发,无需额外氢受体的通用且原子经济的1,1-二硼基烷烃合成方法。我们成功的关键在于使用了储量丰富的锆基催化剂,它能实现自相矛盾的反应活性(脱氢硼化和硼氢化)之间的平衡。我们的方法避免了使用过量的另一种烯烃作为氢受体,而这在其他已报道的体系中是必需的。此外,诸如之前不发生反应的简单长链脂肪族烯烃等底物,在我们的体系中也能进行1,1-二硼化反应。值得注意的是,内烯烃前所未有的1,1-二硼化反应使得1,1-二硼基烷烃的制备成为可能。