Palladium-Catalyzed Intermolecular [4+1] Spiroannulation by C(sp3 )-H Activation and Naphthol Dearomatization.
Palladium-Catalyzed Intermolecular [4+1] Spiroannulation by C(sp3 )-H Activation and Naphthol Dearomatization.
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DOI：
10.1002/anie.201813202
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发表时间：
2018-12
影响因子：
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通讯作者：
Bojun Tan;Lu Bai;Pin Ding;Jingjing Liu;Yaoyu Wang;X. Luan
中科院分区：
文献类型：
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作者：
Bojun Tan;Lu Bai;Pin Ding;Jingjing Liu;Yaoyu Wang;X. Luan
采用C（sp3）-H活化/萘酚脱芳构化方法，发展了一种新的钯催化[4+1]螺环化反应。这两个芳基卤化物的双分子多米诺反应是通过一系列环化促进的C（sp3）-H活化，联芳基交叉偶联和萘酚脱芳构化来实现的，从而使一类新的螺环分子的快速组装以良好的产率具有广泛的官能团耐受性。初步的机理研究表明，C-H裂解可能参与的速率决定步骤，和五元钯被确定为分子间偶联的关键中间体。
A novel palladium-catalyzed [4+1] spiroannulation was developed by using a C(sp3 )-H activation/naphthol dearomatization approach. This bimolecular domino reaction of two aryl halides was realized through a sequence of cyclometallation-facilitated C(sp3 )-H activation, biaryl cross-coupling, and naphthol dearomatization, thus rendering the rapid assembly of a new class of spirocyclic molecules in good yields with broad functional-group tolerance. Preliminary mechanistic studies indicate that C-H cleavage is likely involved in the rate-determining step, and a five-membered palladacycle was identified as the key intermediate for the intermolecular coupling.