Synthetic Strategy for AB2-Type Arsines via Bidentate Dithiolate Leaving Groups
Synthetic Strategy for AB2-Type Arsines via Bidentate Dithiolate Leaving Groups
复制标题
双齿二硫醇盐离去基团合成AB2型胂的策略
DOI：
10.1021/acs.inorgchem.2c01974
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发表时间：
2022
影响因子：
4.6
通讯作者：
Naka Kensuke
中科院分区：
文献类型：
--
作者：
Sumida Akifumi;Imoto Hiroaki;Naka Kensuke
尽管砷配体具有几种过渡金属催化反应的潜力，但它们的多样性很差。在这项工作中，我们开发了一种有效的合成方法AB 2型配体，这是一个典型的基序磷系统，例如，在Buchwald配体。将1，2-苯二硫醇引入三溴胂中降低了三个反应位点中的两个的反应性。在与第一亲核试剂的取代反应涉及溴的消除之后，与第二亲核试剂的取代反应通过消除二硫醇盐阴离子产生AB 2型胂。在所获得的各种类型的AB 2型胂中，arsa-Buchwald配体，其为Buchwald配体的砷类似物，被应用于Suzuki-Miyaura交叉偶联反应。一些arsa-Buchwald配体显示出与众所周知的Buchwald配体SPhos相当的活性。此外，在露天条件下，SPhos的砷类似物显示出比SPhos更高的活性和稳定性。
Despite their potential for several transition-metal-catalyzed reactions, arsenic ligands are poorly diversified. In this work, we developed an efficient synthetic methodology for AB2-type ligands, which is a typical motif in phosphorus systems, for example, in Buchwald ligands. The introduction of 1,2-benzenedithiol to tribromoarsine reduces the reactivity of two of the three reaction sites. After the substitution reaction with the first nucleophile involving the elimination of bromide, the substitution reaction with the second nucleophile produced AB2-type arsines through the elimination of the dithiolate anion. Among the various types of obtained AB2-type arsines, the arsa-Buchwald ligands, which are arsenic analogues of Buchwald ligands, were applied to the Suzuki–Miyaura cross-coupling reaction. Some of the arsa-Buchwald ligands showed activity comparable to that of the well-known Buchwald ligand, SPhos. Furthermore, the arsenic analogue of SPhos showed higher activity and stability than SPhos under open-air conditions.