Rh(III)- and Ir(III)-Catalyzed C鈥揌 Alkynylation of Arenes under Chelation Assistance

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• 作者：Fang Xie ; Zisong Qi ; Songjie Yu ; Xingwei Li
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：March 26, 2014
• 年：2014
• 卷：136
• 期：12
• 页码：4780-4787
• 全文大小：522K
• 年卷期：v.136,no.12(March 26, 2014)
• ISSN：1520-5126

文摘

An efficient Rh(III)- and Ir(III)-catalyzed, chelation-assisted C鈥揌 alkynylation of a broad scope of (hetero)arenes has been developed using hypervalent iodine-alkyne reagents. Heterocycles, N-methoxy imines, azomethine imines, secondary carboxamides, azo compounds, N-nitrosoamines, and nitrones are viable directing groups to entail ortho C鈥揌 alkynylation. The reaction proceeded under mild conditions and with controllable mono- and dialkynylation selectivity when both mono- and dialkynylation was observed. Rh(III) and Ir(III) catalysts exhibited complementary substrate scope in this reaction. The synthetic applications of the coupled products have been demonstrated in subsequent derivatization reactions. Some mechanistic studies have been conducted, and two Rh(III) complexes have been established as key reaction intermediates. The current C鈥揌 alkynylation system complements those previously reported under gold or palladium catalysis using hypervalent iodine reagents.