Metallaphotoredox catalysis for multicomponent coupling reactions

Lu, Fu‐Dong; He, Gui-Feng; Lu, Liang‐Qiu; Xiao, Wen‐Jing

doi:10.1039/d1gc00993a

“…Alkyne and alkene moieties are ubiquitous building blocks for photochemical transformations, given their widespread natural and synthetic occurrence. [1][2][3][4][5][6][7] Therefore, reactions aimed at combining them by creating a new CÀ C bond are an integral part of the path towards molecular complexity. Along with the generally accepted CÀ C cross-coupling reactions involving unsaturated hydrocarbons with leaving groups (Sonogashira, Suzuki, Heck and other reactions), alternative methods of direct atom-economical ene-ene, ene-yne and yne-yne couplings were developed.…”

Section: Introductionmentioning

confidence: 99%

Intermolecular Photocatalytic Chemo‐, Stereo‐ and Regioselective Thiol–Yne–Ene Coupling Reaction

Burykina

¹

,

Kobelev

²

,

Shlapakov

³

et al. 2022

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The first example of an intermolecular thiolyne-ene coupling reaction is reported for the one-pot construction of CÀ S and CÀ C bonds. Thiol-yne-ene coupling opens a new dimension in building molecular complexity to access densely functionalized products. The employment of Eosin Y/DBU/MeOH photocatalytic system suppresses hydrogen atom transfer (HAT) and associative reductant upconversion (via CÀ S threeelectron σ-bond formation). Investigation of the reaction mechanism by combining online ESI-UHRMS, EPR spectroscopy, isotope labeling, determination of quantum yield, cyclic voltammetry, Stern-Volmer measurements and computational modeling revealed a unique photoredox cycle with four radical-involving stages. As a result, previously unavailable products of the thiol-yneene reaction were obtained in good yields with high selectivity. They can serve as stable precursors for synthesizing synthetically demanding activated 1,3-dienes.

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“…Metallaphotoredox catalysis has gained momentum as a powerful synthetic tool 38 – 40 , in particular by allowing alcohols 41 – 43 , primary amines 44 , 45 and aldehydes 46 – 48 to be used as adaptative C( sp 3 ) handles in C-C bond-formations. These approaches generally rely on the conversion of traditionally inert chemical functionality into groups susceptible to single-electron activation.…”

Section: Introductionmentioning

confidence: 99%

Dihydroquinazolinones as adaptative C(sp3) handles in arylations and alkylations via dual catalytic C–C bond-functionalization

Lv

¹

,

Abrams

²

,

Martı́n

³

2022

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C–C bond forming cross-couplings are convenient technologies for the construction of functional molecules. Consequently, there is continual interest in approaches that can render traditionally inert functionality as cross-coupling partners, included in this are ketones which are widely-available commodity chemicals and easy to install synthetic handles. Herein, we describe a dual catalytic strategy that utilizes dihydroquinazolinones derived from ketone congeners as adaptative one-electron handles for forging C(sp3) architectures via α C–C cleavage with aryl and alkyl bromides. Our approach is achieved by combining the flexibility and modularity of nickel catalysis with the propensity of photoredox events for generating open-shell reaction intermediates. This method is distinguished by its wide scope and broad application profile––including chemical diversification of advanced intermediates––, providing a catalytic technique complementary to existing C(sp3) cross-coupling reactions that operates within the C–C bond-functionalization arena.

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“…Alkyne and alkene moieties are ubiquitous building blocks for photochemical transformations, given their widespread natural and synthetic occurrence [1–7] . Therefore, reactions aimed at combining them by creating a new C−C bond are an integral part of the path towards molecular complexity.…”

Section: Introductionmentioning

confidence: 99%

Intermolecular Photocatalytic Chemo‐, Stereo‐ and Regioselective Thiol–Yne–Ene Coupling Reaction

Burykina

¹

,

Kobelev

²

,

Shlapakov

³

et al. 2022

View full text Add to dashboard Cite

The first example of an intermolecular thiolyne-ene coupling reaction is reported for the one-pot construction of CÀ S and CÀ C bonds. Thiol-yne-ene coupling opens a new dimension in building molecular complexity to access densely functionalized products. The employment of Eosin Y/DBU/MeOH photocatalytic system suppresses hydrogen atom transfer (HAT) and associative reductant upconversion (via CÀ S threeelectron σ-bond formation). Investigation of the reaction mechanism by combining online ESI-UHRMS, EPR spectroscopy, isotope labeling, determination of quantum yield, cyclic voltammetry, Stern-Volmer measurements and computational modeling revealed a unique photoredox cycle with four radical-involving stages. As a result, previously unavailable products of the thiol-yneene reaction were obtained in good yields with high selectivity. They can serve as stable precursors for synthesizing synthetically demanding activated 1,3-dienes.

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Metallaphotoredox catalysis for multicomponent coupling reactions

Abstract: The combination of photoredox and transition metal catalysis, which is termed metallaphotoredox catalysis, is a powerful platform for building complex molecules under mild conditions. In particular, metallaphotoredox-catalyzed multicomponent coupling reactions,...

Cited by 76 publications

References 139 publications

Intermolecular Photocatalytic Chemo‐, Stereo‐ and Regioselective Thiol–Yne–Ene Coupling Reaction

Intermolecular Photocatalytic Chemo‐, Stereo‐ and Regioselective Thiol–Yne–Ene Coupling Reaction

Dihydroquinazolinones as adaptative C(sp3) handles in arylations and alkylations via dual catalytic C–C bond-functionalization

Intermolecular Photocatalytic Chemo‐, Stereo‐ and Regioselective Thiol–Yne–Ene Coupling Reaction

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