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Review
. 2021 Jan 25;60(4):1714-1726.
doi: 10.1002/anie.202007668. Epub 2020 Sep 1.

Stereoinduction in Metallaphotoredox Catalysis

Alexander Lipp  1 , Shorouk O Badir  1 , Gary A Molander  1
Affiliations
Review

Stereoinduction in Metallaphotoredox Catalysis

Alexander Lipp et al. Angew Chem Int Ed Engl. .

Abstract

Metallaphotoredox catalysis has evolved into an enabling platform to construct C(sp3 )-hybridized centers under remarkably mild reaction conditions. The cultivation of abundant radical precursor feedstocks has significantly increased the scope of transition-metal-catalyzed cross-couplings, especially with respect to C(sp2 )-C(sp3 ) linkages. In recent years, considerable effort has been devoted to understanding the origin of stereoinduction in dual catalytic processes. In this context, Ni- and Cu-catalyzed transformations have played a predominant role exploiting this mode of catalysis. Herein, we provide a critical overview on recent progress in enantioselective bond formations enabled by Ni- and Cu-catalyzed manifolds. Furthermore, selected stereochemical control elements within the realm of diastereoselective transformations are discussed.

Keywords: cross-coupling; energy transfer; photocatalysis; radical precursors; stereoinduction.

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Conflict of interest statement

Conflict of interest

The authors declare no conflict of interest.

Figures

Figure 1.
Figure 1.
A) Photocatalytic quenching cycles and B) three common photoredox catalysts.
Scheme 1.
Scheme 1.
Enantioselective photoredox/Ni dual-catalyzed cross-coupling of benzyltrifluoroborates.
Scheme 2.
Scheme 2.
Enantioselective photoredox/Ni dual-catalyzed cross-coupling of A) α-trifluoromethyltrifluoroborates and B) α-alkoxymethyltrifluoroborates.
Scheme 3.
Scheme 3.
Enantioselective photoredox/Ni dual-catalyzed desymmetrization of A) cyclic meso anhydrides and B) diols.
Scheme 4.
Scheme 4.
Enantioselective photoredox/Ni dual-catalyzed decarboxylative arylations.
Scheme 5.
Scheme 5.
Enantioselective photoredox/Ni dual-catalyzed C(sp3)-H arylation.
Scheme 6.
Scheme 6.
Enantioselective photoredox/Ni dual-catalyzed C(sp3)-H arylation.
Scheme 7.
Scheme 7.
A) Enantioselective photoredox/Ni dual-catalyzed arylation of α-chloro esters and B) photoinduced enantioselective oxidation of β-ketoesters and β-ketoamides.
Scheme 8.
Scheme 8.
Enantioselective photochemical Ni-catalyzed acylation using 1,4-DHPs.
Scheme 9.
Scheme 9.
Enantioselective photoredox/Ni dual-catalyzed 1,2-carbodifunctionalization of carbamoyl chloride-tethered alkenes.
Scheme 10.
Scheme 10.
Mechanism involving photoexcitation of a CuI complex and reductive elimination from CuIII.
Scheme 11.
Scheme 11.
Enantioselective C-N cross-coupling of tertiary α-chloroamides with carbazoles and indoles.
Scheme 12.
Scheme 12.
Interposing a Giese-type addition prior to formation of the CuIII intermediate enables A) cyanation/fluoroalkylation and B) alkylation/alkynylation or arylation/alkynylation of alkenes.
Scheme 13.
Scheme 13.
Enantioselective alkylation of N-sulfonylimines and selected ketimines.
Scheme 14.
Scheme 14.
Enantioselective α-aminoalkylation of N-acylhydrazones.
Scheme 15.
Scheme 15.
Enantioselective alkynylation of N-aryl-1,2,3,4-tetrahydroisoquinolines.
Scheme 16.
Scheme 16.
Proposed mechanism for Cu/photoredox dual-catalyzed enantioselective cyanations.
Scheme 17.
Scheme 17.
Enantioselective cyanations using redox-active esters as radical precursors.
Scheme 18.
Scheme 18.
Enantioselective cyanations using A) oxime esters and B) N-alkoxypyridinium salts as radical precursors.
Scheme 19.
Scheme 19.
Enantioselective alkylation of N-sulfonylimines.
Scheme 20.
Scheme 20.
Diastereoselective photoredox/Ni dual-catalyzed 1,2-amidoacylation.
Scheme 21.
Scheme 21.
Diastereoselective photoredox/Ni dual-catalyzed arylation of saccharide-based DHPs.
Scheme 22.
Scheme 22.
Diastereoselective photoredox/Ni dual-catalyzed alkylarylation of alkynes.
Scheme 23.
Scheme 23.
Diastereoselective photoredox/Ni dual-catalyzed 1,2-carbosulfonylation of alkynes.
See this image and copyright information in PMC

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