Photoinduced Cobalt-Catalyzed Desymmetrization of Dialdehydes to Access Axial Chirality

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(12), P. 6944 - 6952

Published: March 15, 2023

Enantioselective metallaphotoredox catalysis, which combines photoredox catalysis and asymmetric transition-metal has become an effective approach to achieve stereoconvergence under mild conditions. Although many impressive synthetic approaches have been developed access central chirality, the construction of axial chirality by still remains underexplored. Herein, we report two visible light-induced cobalt-catalyzed reductive couplings biaryl dialdehydes synthesize axially chiral aldehydes (60 examples, up 98% yield, >19:1 dr, >99% ee). This protocol shows good functional group tolerance, broad substrate scope, excellent diastereo- enantioselectivity.

Language: Английский

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Axially chiral alkenes: Atroposelective synthesis and applications

Tetrahedron Chem, Journal Year: 2022, Volume and Issue: 1, P. 100009 - 100009

Published: March 1, 2022

Axial chirality is historically epitomized by biaryl compounds containing rotationally impeded aryl-aryl linkage. As the field of atroposelective catalysis advances, synthesis and application less common scaffolds such as alkenes have now come to fore. The manifestation axial in aryl was hypothesized 1928 first resolution achieved nearly a decade later. However, catalytic asymmetric construction axially chiral open-chain appeared only 2017 which ushered renewed focus on these structures. In principle, possess an alkene group tethered at one end stereogenic axis, greatly reduces overall rigidity. To date, atropisomers with C (vinyl)-C (aryl) (vinyl)-heteroatom bond been reported. Considering rapid growth synthetic utility alkenes, this review intends provide historical overview discusses new developments. It hope that timely discussion would motivate continued nascent field.

Language: Английский

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Synthesis of axially chiral alkenylboronates through combined copper- and palladium-catalysed atroposelective arylboration of alkynes

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(2), P. 140 - 151

Published: Jan. 5, 2023

Language: Английский

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Atroposelective catalysis

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(7), P. 497 - 517

Published: June 18, 2024

Language: Английский

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Accessing chiral sulfones bearing quaternary carbon stereocenters via photoinduced radical sulfur dioxide insertion and Truce–Smiles rearrangement

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Nov. 18, 2022

Abstract From the viewpoint of synthetic accessibility and functional group compatibility, photoredox-catalyzed sulfur dioxide insertion strategy enables in situ generation functionalized sulfonyl radicals from easily accessible starting materials under mild conditions, thereby conferring broader application potential. Here we present two complementary photoinduced systems to trigger radical asymmetric Truce–Smiles rearrangements for preparing a variety chiral sulfones that bear quaternary carbon stereocenter. This protocol features broad substrate scope excellent stereospecificity. Aside scalability, introduction stereocenter at position β bioactive molecule-derived further demonstrates practicality potential this methodology.

Language: Английский

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Photoredox-Catalyzed α-Sulfonylation of Ketones from Sulfur Dioxide and Thianthrenium Salts

Organic Letters, Journal Year: 2022, Volume and Issue: 24(15), P. 2955 - 2960

Published: April 13, 2022

A photoredox-catalyzed sulfonylation of silyl enol ethers with DABCO·(SO2)2 and thianthrenium salts is achieved, providing diverse β-keto sulfones in moderate to good yields. This protocol features easily accessible starting materials functional group compatibility, enabling the introduction various functionalized sulfonyl groups into ketones. Furthermore, as one important industrial raw materials, methanol can be employed methyl source prepare α-methylsulfonated ketones through a intermediate for first time.

Language: Английский

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Access to chiral β-sulfonyl carbonyl compounds via photoinduced organocatalytic asymmetric radical sulfonylation with sulfur dioxide

Chemical Science, Journal Year: 2022, Volume and Issue: 13(30), P. 8834 - 8839

Published: Jan. 1, 2022

An organocatalytic enantioselective radical reaction of potassium alkyltrifluoroborates, DABCO·(SO

Language: Английский

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Control of Axial Chirality through NiH-Catalyzed Atroposelective Hydrofunctionalization of Alkynes

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(6), P. 3841 - 3846

Published: March 3, 2023

Catalytic asymmetric hydrofunctionalization of alkenes is a well-established method with which to construct complex C(sp3)-enriched molecules central chirality. In contrast, the use catalytic abundant alkyne substrates produce valuable multisubstituted axial chirality remains largely unexplored. Here, we report general procedure this type catalyzed by Ni(II) salts and employing structurally simple chiral PyrOx ligand. A wide variety diverse atropisomeric styrenes have been obtained from hydroarylation alkynes high efficiency, complete Z-selectivity, excellent enantioselectivity.

Language: Английский

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Asymmetric sulfonylation with sulfur dioxide surrogates: a new access to enantiomerically enriched sulfones

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(26), P. 3821 - 3826

Published: Jan. 1, 2023

In this highlight, we survey recent exciting advances in asymmetric sulfonylation by using sulfur dioxide surrogates, and discuss induction modes, reaction mechanisms, substrate scope opportunities for further studies.

Language: Английский

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Synthetic strategies and mechanistic studies of axially chiral styrenes

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(6), P. 100594 - 100594

Published: April 6, 2023

Language: Английский

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