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      Photochemical activity of a key donor-acceptor complex can drive stereoselective catalytic α-alkylation of aldehydes.

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          Abstract

          Asymmetric catalytic variants of sunlight-driven photochemical processes hold extraordinary potential for the sustainable preparation of chiral molecules. However, the involvement of short-lived electronically excited states inherent to any photochemical reaction makes it challenging for a chiral catalyst to dictate the stereochemistry of the products. Here, we report that readily available chiral organic catalysts, with well-known utility in thermal asymmetric processes, can also confer a high level of stereocontrol in synthetically relevant intermolecular carbon-carbon bond-forming reactions driven by visible light. A unique mechanism of catalysis is proposed, wherein the catalyst is involved actively in both the photochemical activation of the substrates (by inducing the transient formation of chiral electron donor-acceptor complexes) and the stereoselectivity-defining event. We use this approach to enable transformations that are extremely difficult under thermal conditions, such as the asymmetric α-alkylation of aldehydes with alkyl halides, the formation of all-carbon quaternary stereocentres and the control of remote stereochemistry.

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          Most cited references30

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          Visible light photoredox catalysis: applications in organic synthesis.

          The use of visible light sensitization as a means to initiate organic reactions is attractive due to the lack of visible light absorbance by organic compounds, reducing side reactions often associated with photochemical reactions conducted with high energy UV light. This tutorial review provides a historical overview of visible light photoredox catalysis in organic synthesis along with recent examples which underscore its vast potential to initiate organic transformations.
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            Merging photoredox catalysis with organocatalysis: the direct asymmetric alkylation of aldehydes.

            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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              Asymmetric enamine catalysis.

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                Author and article information

                Journal
                Nat Chem
                Nature chemistry
                1755-4349
                1755-4330
                Sep 2013
                : 5
                : 9
                Affiliations
                [1 ] 1] Institute of Chemical Research of Catalonia, Avenguda Països Catalans 16-43007 Tarragona, Spain [2].
                Article
                nchem.1727
                10.1038/nchem.1727
                23965676
                8e61507d-f697-4092-a54a-d4b332025c6c
                History

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