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. 2012 May 16;134(19):8094-7.
doi: 10.1021/ja3030164. Epub 2012 May 2.

Catalytic asymmetric α-acylation of tertiary amines mediated by a dual catalysis mode: N-heterocyclic carbene and photoredox catalysis

Daniel A DiRocco  1 , Tomislav Rovis
Affiliations

Catalytic asymmetric α-acylation of tertiary amines mediated by a dual catalysis mode: N-heterocyclic carbene and photoredox catalysis

Daniel A DiRocco et al. J Am Chem Soc. .

Abstract

Cross-coupling reactions are among the most widely utilized methods for C-C bond formation; however, the requirement of preactivated starting materials still presents a major limitation. Methods that take direct advantage of the inherent reactivity of the C-H bond offer an efficient alternative to these methods, negating the requirement for substrate preactivation. In this process, two chemically distinct activation events culminate in the formation of the desired C-C bond with loss of H(2) as the only byproduct. Herein we report the catalytic asymmetric α-acylation of tertiary amines with aldehydes facilitated by the combination of chiral N-heterocyclic carbene catalysis and photoredox catalysis.

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Figures

Figure 1
Figure 1
Proposed Dual Catalysis Mode
Figure 2
Figure 2. X-Ray Structure of Isolated Catalyst Resting State 5
Ellipsoids drawn at the 75% probability level.
Scheme 1
Scheme 1
Proposed Catalytic Cycles
See this image and copyright information in PMC

References

    1. De Meijere A, Diederich F, editors. Metal Catalyzed Cross-Coupling Reactions. 2nd Ed. Wiley-VCH; Weinheim, Germany: 2004.
    1. Crabtree RH, editor. Selective Functionalization of C-H Bonds; Thematic Issue in Chem. Rev. 2010;110:575. - PubMed
    1. Davies HML, Du Bois J, Yu J-Q, editors. C–H Functionalization in organic synthesis, Thematic Issue in Chem. Soc. Rev. 2011;40:1855. - PubMed
    1. Stuart DR, Fagnou K. Science. 2007;316:1172. - PubMed
    1. Yeung CS, Dong VM. Chem. Rev. 2011;111:1215. - PubMed

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