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. 2008 Oct 3;322(5898):77-80.
doi: 10.1126/science.1161976. Epub 2008 Sep 4.

Merging photoredox catalysis with organocatalysis: the direct asymmetric alkylation of aldehydes

David A Nicewicz  1 , David W C MacMillan
Affiliations

Merging photoredox catalysis with organocatalysis: the direct asymmetric alkylation of aldehydes

David A Nicewicz et al. Science. .

Abstract

Photoredox catalysis and organocatalysis represent two powerful fields of molecule activation that have found widespread application in the areas of inorganic and organic chemistry, respectively. We merged these two catalysis fields to solve problems in asymmetric chemical synthesis. Specifically, the enantioselective intermolecular alpha-alkylation of aldehydes has been accomplished using an interwoven activation pathway that combines both the photoredox catalyst Ru(bpy)3Cl2 (where bpy is 2,2'-bipyridine) and an imidazolidinone organocatalyst. This broadly applicable, yet previously elusive, alkylation reaction is now highly enantioselective and operationally trivial.

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Figures

Fig. 1
Fig. 1
Merging amine catalysis and organometallic photoredox catalysis to enable asymmetric organic transformations. Me, methyl; R, generic organic substituent; FG, electron-withdrawing functional group.
Fig. 2
Fig. 2
Merging photoredox catalysis with organocatalysis. Proposed mechanism. t-Bu, tert-butyl.
See this image and copyright information in PMC

Comment in

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