Rh(III)-Catalyzed Redox-Neutral C-H Activation/[3 + 2] Annulation of N-Phenoxy Amides with Propargylic Monofluoroalkynes.
Rh(III)-Catalyzed Redox-Neutral C-H Activation/[3 + 2] Annulation of N-Phenoxy Amides with Propargylic Monofluoroalkynes.
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DOI：
10.1021/acs.orglett.1c00418
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发表时间：
2021-03
期刊：
影响因子：
5.2
通讯作者：
Xiuhua Zhong;Shuang-zheng Lin;Hui Gao;Fu-Xiaomin Liu;Zhi Zhou;Wei Yi
中科院分区：
文献类型：
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作者：
Xiuhua Zhong;Shuang-zheng Lin;Hui Gao;Fu-Xiaomin Liu;Zhi Zhou;Wei Yi
采用Rh（III）催化的高效氧化还原中性n -苯氧基酰胺与丙基单氟炔的C-H活化/[3 + 2]环化反应，得到了具有有趣的α-季碳中心的3-烷基二氢苯并呋喃。结合实验和计算机制研究表明，Rh(III)-Rh(V)-Rh（III）催化途径/非催化的分子内[H···F]键辅助的SN2'型取代级联可能参与了催化循环，从而实现了良好的位点/区域选择性，具有广泛的底物/官能团相容性，包括在3位上完全保留高应变环丁基结构。
An efficient and redox-neutral Rh(III)-catalyzed C-H activation/[3 + 2] annulation of N-phenoxy amides with propargylic monofluoroalkynes has been realized to afford 3-alkylidene dihydrobenzofurans with an interesting α-quaternary carbon center. Combined experimental and computational mechanistic studies revealed that a Rh(III)-Rh(V)-Rh(III) catalytic pathway/uncatalyzed intramolecular [H···F] bonding-assisted SN2'-type substitution cascade might be involved in the catalytic cycle, thereby enabling an excellent site-/regioselectivity with broad substrate/functional group compatibility, including the complete retention of the highly strained cyclobutyl structure in the 3-position.