天津师范大学王超团队报道了对映选择性镍催化非活化烯烃的1,2-硼炔基化反应。相关研究成果于2024年6月12日发表于国际一流学术期刊《美国化学会杂志》。

烯烃与硼试剂的对映选择性三组分双官能化，是组装三维手性有机硼化合物的一种有吸引力的策略。然而，区域和对映体控制构成了这些转化的关键挑战，这主要需要使用活化的共轭烯烃。

该文中，研究人员通过利用各种羰基导向基团，包括酰胺、磺酰胺、酮和酯，成功地实现了未活化烯烃的镍催化的1，2-硼基烷基化，以使硼实体和sp片段能够同时通过双键结合。这些产品含有具有正交合成反应性的硼基、炔基和羰基官能团，为进一步衍生提供了三个途径，以获得有价值的中间体。通过药物相关分子的后期修饰，强调了这种配体使能的不对称方案的实用性。

附：英文原文

Title: Enantioselective Ni-Catalyzed 1,2-Borylalkynylation of Unactivated Alkenes

Author: Jie Huang, Xueyuan Yan, Xuanyu Liu, Zhengyang Chen, Tao Jiang, Lanlan Zhang, Guodong Ju, Genping Huang, Chao Wang

Issue&Volume: June 12, 2024

Abstract: Enantioselective three-component difunctionalization of alkenes with boron reagents represents an attractive strategy for assembling three-dimensional chiral organoboron compounds. However, regio- and enantiocontrol comprise the pivot challenges in these transformations, which predominantly require the use of activated conjugated alkenes. Herein, by utilizing various carbonyl directing groups, including amides, sulfinamides, ketones, and esters, we succeed in realizing a nickel-catalyzed 1,2-borylalkynylation of unactivated alkenes to enable the simultaneous incorporation of a boron entity and an sp-fragment across the double bond. The products contain boryl, alkynyl, and carbonyl functional groups with orthogonal synthetic reactivities, offering three handles for further derivatization to access valuable intermediates. The utility of this ligand-enabled asymmetric protocol has been highlighted through the late-stage decoration of drug-relevant molecules.

DOI: 10.1021/jacs.4c03022

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c03022