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

被引：99

作者：

Nicholls, Thomas P. ^{[1
]}

Constable, Grace E. ^{[1
]}

Robertson, Johnathon C. ^{[1
]}

Gardiner, Michael G. ^{[1
]}

Bissember, Alex C. ^{[1
]}

机构：

[1] Univ Tasmania, Sch Phys Sci Chem, Hobart, Tas 7001, Australia

来源：

ACS CATALYSIS | 2016年 / 6卷 / 01期

关键词：

photocatalysis; Cu(dap)(2)]Cl; trifluoroacetic acid; aerobic oxidation; visible light; TRANSFER RADICAL-ADDITION; LIGHT PHOTOREDOX CATALYSIS; ELECTRON-TRANSFER; PHOTOCHEMICAL-REACTIONS; TRIFLUOROACETIC-ACID; TERTIARY ANILINES; MOLECULAR-OXYGEN; COPPER(I); PHENANTHROLINE; OXIDATION;

D O I：

10.1021/acscatal.5b02014

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We have exploited a bis(1,10-phenanthroline)copper(I) visible light photocatalyst (VLP), [Cu(dap)(2)](+), to effect the direct alpha-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, I -a] pyrrolo[3,4-dquinoline 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.

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页码：451 / 457

页数：7

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