1,3-Difunctionalizations of [1.1.1]Propellane via 1,2-Metallate Rearrangements of Boronate Complexes
1,3-Difunctionalizations of [1.1.1]Propellane via 1,2-Metallate Rearrangements of Boronate Complexes
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[1.1.1]丙烷通过硼酸盐配合物的 1,2-金属盐重排进行 1,3-双官能化
DOI：
10.1002/ange.201914875
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发表时间：
2020
影响因子：
--
通讯作者：
Yu S
中科院分区：
文献类型：
--
作者：
Yu S
1,3 -二取代双环[1.1.1]戊烷（bcp）是有价值的对取代芳香环的生物异构体。生成这些结构的最直接途径是通过[1.1.1]推进剂的多组分开环反应。然而，与这些转化相关的挑战意味着双功能化BCP更常通过与BCP卤化物中间体的多步反应序列来制备。在此，我们报道了[1.1.1]丙烷与有机金属试剂、有机硼酯和各种亲电试剂的三组分和四组分1,3双官能化反应。这个过程是通过用硼酯捕获中间的BCP -金属来形成硼酸盐配合物来实现的，硼酸盐配合物是一种多用途的中间体，其亲电诱导的1,2 -金属重排化学可以实现广泛的C - C键形成反应。
1,3‐Disubstituted bicyclo[1.1.1]pentanes (BCPs) are valuable bioisosteres ofpara‐substituted aromatic rings. The most direct route to these structures is via multicomponent ring‐opening reactions of [1.1.1]propellane. However, challenges associated with these transformations mean that difunctionalized BCPs are more commonly prepared by multistep reaction sequences with BCP‐halide intermediates. Herein, we report three‐ and four‐component 1,3‐difunctionalizations of [1.1.1]propellane with organometallic reagents, organoboronic esters, and a variety of electrophiles. This process is achieved by trapping intermediate BCP‐metal species with boronic esters to form boronate complexes, which are versatile intermediates whose electrophile‐induced 1,2‐metallate rearrangement chemistry enables a broad range of C−C bond‐forming reactions.