Aryne 1,4-Disubstitution and Remote Diastereoselective 1,2,4- Trisubstitution via a Nucleophilic Annulation-[5,5]-Sigmatropic Rearrangement Process
Aryne 1,4-Disubstitution and Remote Diastereoselective 1,2,4- Trisubstitution via a Nucleophilic Annulation-[5,5]-Sigmatropic Rearrangement Process
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通过亲核成环-[5,5]-Sigmatropic 重排过程进行芳炔 1,4-二取代和远程非对映选择性 1,2,4- 三取代
DOI：
10.1002/anie.202212160
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Yang Li
中科院分区：
文献类型：
--
作者：
Zhonghong Chen;Min Tan;Chunhui Shan;Xiaoling Yuan;Liyuan Chen;Jiarong Shi;Yu Lan;Yang Li
Both aryne 1,4‐disubstitution and 1,2,4‐trifunctionalization were accomplished from tertiary amines bearing a penta‐2,4‐dien‐1‐yl moiety. These transformations could directly incorporate a C−N and a C−C bond para to each other on an aryne intermediate via a sequential nucleophilic addition and [5,5]‐sigmatropic rearrangement. When arynes bearing 3‐tethered electrophiles were employed, a cascade regioselective nucleophilic addition, intramolecular cyclization, and remote diastereoselective [5,5]‐sigmatropic rearrangement process was observed. Our density functional theory (DFT) calculations revealed that hydrogen‐bonding interactions between two C−H hydrogens on the penta‐2,4‐dien‐1‐yl chain and the oxygen anion generated upon N‐nucleophilic annulation reaction in the [5,5]‐sigmatropic rearrangement step is responsible for the remote diastereoselective control in this reaction system.
