扬州大学段伟良课题组近日在P-立体定向的仲膦硼烷的不对称合成研究中取得进展。这一研究成果于2021年4月9日发表在国际顶尖学术期刊《美国化学会志》上。

在该研究中，通过新开发的不对称双膦钳形镍配合物将伯膦不对称加成到缺乏电子的烯烃上，研究人员首次实现了P-立体定向的仲膦硼烷的高对映选择性催化合成。通过该方法合成P-立体定向的仲膦硼烷收率为57 ~ 92%，ee值高达99%，dr大于20:1。

研究人员表示，在P-C键形成后，后续使用卤代烃进行烷基化反应可为获取具有不同官能团的P-手性化合物提供一种实用的途径。

附：英文原文

Title: Asymmetric Synthesis of P-Stereogenic Secondary Phosphine-Boranes by an Unsymmetric Bisphosphine Pincer-Nickel Complex

Author: Chuanyong Wang, Kesheng Huang, Jie Ye, Wei-Liang Duan

Issue&Volume: April 9, 2021

Abstract: The first highly enantioselective catalytic synthesis of P-stereogenic secondary phosphine-boranes was realized by the asymmetric addition of primary phosphine to electron-deficient alkenes with a newly developed unsymmetric bisphosphine (PCP′) pincer-nickel complex. Various P-stereogenic secondary phosphine-boranes were obtained in 57–92% yields with up to 99% ee and >20:1 dr. The follow-up alkylation upon P–C bond formation with alkyl halides provided a practical way to access P-chiral compounds with diverse functional groups.

DOI: 10.1021/jacs.1c02772

Source: https://pubs.acs.org/doi/10.1021/jacs.1c02772