anti‐Selective Borylstannylation of Alkynes with (o‐Phenylenediaminato)borylstannanes by a Radical Mechanism
anti‐Selective Borylstannylation of Alkynes with (o‐Phenylenediaminato)borylstannanes by a Radical Mechanism
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通过自由基机制用（邻苯二胺）硼基锡烷对炔烃进行反选择性硼基锡烷基化
DOI：
10.1002/anie.202201883
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Yasuda Makoto
中科院分区：
文献类型：
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作者：
Suzuki Kensuke;Sugihara Naoki;Nishimoto Yoshihiro;Yasuda Makoto
我们首次用邻苯二胺基硼基锡烷实现了炔的三硼基锡烷基化反应。该反应通过自由基机理得到了具有良好区域和立体选择性的1-硼基-2-锡烷基烯烃。这种反加成方式与在过渡金属催化的硼基锡烷基化过程中获得的锡烯选择性形成鲜明对比。温和的自由基条件使广泛的底物范围，和各种类型的芳香族和脂肪族炔是适用的。通过对反应机理的DFT计算，阐明了区域和立体选择性的来源。将硼基锡烷基化产物应用于交叉偶联或均偶联反应提供了容易获得三芳基乙烯或双硼基丁二烯的途径。
We have achieved the firstanti‐borylstannylation of alkynes by using (o‐phenylenediaminato)borylstannanes. This reaction afforded 1‐boryl‐2‐stannylalkenes with excellent regio‐ and stereoselectivity by a radical mechanism. Thisanti‐addition manner is in sharp contrast to thesyn‐selectivity obtained during transition metal‐catalyzed borylstannylation. The mild radical conditions enabled a broad substrate scope, and various types of aromatic and aliphatic alkynes were applicable. The origin of regio‐ and stereoselectivity was elucidated by DFT calculation of the reaction mechanism. The application of the borylstannylation products to cross‐ or homocoupling reactions provided ready access to either triarylethenes or bisborylbutadienes.