Brønsted Acid Cocatalysis in Copper(I)-Photocatalyzed α-Amino C–H Bond Functionalization

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• 作者：Thomas P. Nicholls ; Grace E. Constable ; Johnathon C. Robertson ; Michael G. Gardiner ; Alex C. Bissember
• 刊名：ACS Catalysis
• 出版年：2016
• 出版时间：January 4, 2016
• 年：2016
• 卷：6
• 期：1
• 页码：451-457
• 全文大小：457K
• ISSN：2155-5435

文摘

We have exploited a bis(1,10-phenanthroline)copper(I) visible light photocatalyst (VLP), [Cu(dap)₂]⁺, to effect the direct α-C–H functionalization of amines. To our knowledge, this represents the first example of the oxidation of amines that are ultimately incorporated into synthetic targets by a copper(I) VLP. We have utilized this approach to rapidly prepare unprecedented octahydroisoquinolino[2,1-a]pyrrolo[3,4-c]quinoline frameworks and exploited this process to synthesize a novel aglycone analogue of the natural product incargranine B. Most significantly, our studies suggest that the presence of trifluoroacetic acid (TFA) is crucial in mediating the aerobic oxidative quenching of a putative photoexcited copper(I) species involved in the catalytic cycle.