Palladium(II)‐Catalyzed Regio‐ and Stereoselective Hydroarylation of Diphenylphosphorylallenes with Arylboronic Acids in the Presence of Sodium Hydroxide and Oxygen
Palladium(II)‐Catalyzed Regio‐ and Stereoselective Hydroarylation of Diphenylphosphorylallenes with Arylboronic Acids in the Presence of Sodium Hydroxide and Oxygen
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DOI：
10.1002/adsc.201600160
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发表时间：
2016-09
影响因子：
5.4
通讯作者：
Yang Chen;Dongmei Ma;Feifei Ba;Jing Sun;Tian Liu;Lei Zhu;Mingdong Zhou
中科院分区：
文献类型：
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作者：
Yang Chen;Dongmei Ma;Feifei Ba;Jing Sun;Tian Liu;Lei Zhu;Mingdong Zhou
在氢氧化钠和氧气存在下，钯（II）催化的二苯基磷酰基联烯与芳基硼酸的氢芳基化反应（通过联烯双键的1，2-加成）被开发。区域选择性得到很好的控制，提供2-芳基-3-（二苯基氧膦基）烯烃作为唯一的产品。此外，γ-取代联烯反应的立体选择性也可以很好地控制，导致Z-烯烃的形成。该反应显示出高的取代基负载能力和对各种取代基的耐受性。提出了一种机理，包括芳基硼酸与卤化钯的金属转移，将1，2-联烯双键插入到Pd-Ar键中，以及质子化以提供最终的氢化芳基化产物。
The palladium(II)-catalyzed hydroarylation of diphenylphosphorylallenes (via 1,2-addition of the allenic double bond) with arylboronic acids in the presence of sodium hydroxide and oxygen is developed. The regioselectivities turn out to be well controlled, affording 2-aryl-3-(diphenylphosphinyl)alkenes as the only product. Moreover, the stereoselectivities for reactions of γ-substituted allenes can also be nicely controlled, resulting in the formation of Z-alkenes. The reaction shows high substituent loading capability and tolerance of various substituents. A mechanism, including transmetalation of arylboronic acid with palladium halides, insertion of the 1,2-allenic double bond to the Pd−Ar bond, and protonation to afford the final hydroarylation product is proposed.