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

Thomas P. Nicholls; Grace E. Constable; Johnathon C. Robertson; Michael G. Gardiner; Alex C. Bissember

doi:10.1021/acscatal.5b02014

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

Thomas P. Nicholls, Grace E. Constable, Johnathon C. Robertson, Michael G. Gardiner, Alex C. Bissember

Research output: Contribution to journal › Article › peer-review

114 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	451-457
Number of pages	7
Journal	ACS Catalysis
Volume	6
Issue number	1
Early online date	18 Dec 2015
DOIs	https://doi.org/10.1021/acscatal.5b02014
Publication status	Published - 4 Jan 2016
Externally published	Yes

Keywords

aerobic oxidation
photocatalysis
trifluoroacetic acid
visible light
[Cu(dap)]Cl

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10.1021/acscatal.5b02014Licence: In Copyright

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title = "Br{\o}nsted Acid Cocatalysis in Copper(I)-Photocatalyzed α-Amino C-H Bond Functionalization",

abstract = "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.",

keywords = "aerobic oxidation, photocatalysis, trifluoroacetic acid, visible light, [Cu(dap)]Cl",

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doi = "10.1021/acscatal.5b02014",

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AU - Constable, Grace E.

AU - Robertson, Johnathon C.

AU - Gardiner, Michael G.

AU - Bissember, Alex C.

PY - 2016/1/4

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N2 - 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.

AB - 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.

KW - aerobic oxidation

KW - photocatalysis

KW - trifluoroacetic acid

KW - visible light

KW - [Cu(dap)]Cl

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

Abstract

Keywords

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