Nucleophilic Sulfur Dioxide Insertion Enabled Enantioselective Michael Additions to Access α-chiral Sulfones DOI Creative Commons
Jie Wu, Xinhua Wang, Yun Mao

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 5, 2024

Abstract The asymmetric hydrosulfonylation of α,β-unsaturated carbonyls represents a significant goal in accessing α-chiral sulfones due to its high atom and step efficiency. In contrast the well-established radical sulfonylation, classical Michael addition using sulfonyl anions as nucleophiles for assembling sulfone structures remains elusive challenging. this work, we introduce first time an organocatalytic enantioselective with sulfur dioxide insertion-enabled γ-keto sulfinates nucleophiles, which provides alternative pathway producing highly enantioenriched derivatives excellent economy. methodology showcases innovative mode relay catalysis, where bifunctional organocatalyst containing both tertiary amine hydrogen bond donor sites catalyzes initial nucleophilic insertion subsequent processes two distinct manners. Mechanistic details transformation stereochemical induction were systematically verified through controlled experiments DFT calculations.

Language: Английский

Single-Electron Oxidation-Initiated Enantioselective Hydrosulfonylation of Olefins Enabled by Photoenzymatic Catalysis DOI

Qinglong Shi,

Xiu‐Wen Kang, Zhiyong Liu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2748 - 2756

Published: Jan. 12, 2024

Controlling the enantioselectivity of hydrogen atom transfer (HAT) reactions has been a long-standing synthetic challenge. While recent advances on photoenzymatic catalysis have demonstrated great potential non-natural photoenzymes, all transformations are initiated by single-electron reduction substrate, with only one notable exception. Herein, we report an oxidation-initiated enantioselective hydrosulfonylation olefins using novel mutant gluconobacter ene-reductase (GluER-W100F-W342F). Compared to known systems, our approach does not rely formation electron donor–acceptor complex between substrates and enzyme cofactor simplifies reaction system obviating addition regeneration mixture. More importantly, GluER variant exhibits high reactivity broad substrate scope. Mechanistic studies support proposed mechanism reveal that tyrosine-mediated HAT process is involved.

Language: Английский

Citations

39
Light-promoted photocatalyst-free and redox-neutral hydrosulfonylation of unactivated alkenes using sulfinic acid DOI

Yibo Song,

Cheng Li, Xueyuan Hu

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(11), P. 6578 - 6583

Published: Jan. 1, 2024

Using sulfinic acid as a sulfonyl source, we have developed light-promoted photocatalyst-free alkene hydrosulfonylation reaction without any additives.

Language: Английский

Citations

11
Enantioselective Synthesis of Allylic Sulfones via Rhodium-Catalyzed Direct Hydrosulfonylation of Allenes and Alkynes DOI
Chieh‐Yu Chang, Aaron Aponick

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(25), P. 16996 - 17002

Published: June 14, 2024

A highly regio- and enantioselective hydrosulfonylation using commercially available sodium sulfinates is reported, providing the first direct asymmetric rhodium-catalyzed of allenes/alkynes to synthesize chiral allylic sulfones. Ligand screening studies demonstrated indispensable role C1-symmetric P,N-ligand (Rax,S,S)-StackPhim for achieving both high regioselecitivity (>20:1) enantioselectivity (up 97% ee). Notably, operationally simple method mild conditions allow rapid preparation sulfones with a wide scope functional groups. Moreover, use tert-butyldimethylsilyloxymethanesulfinate enables collective synthesis various sulfone derivatives after transformations protected hydroxymethyl product.

Language: Английский

Citations

8
Copper-Catalyzed Regio- and Enantioselective Protoboration of Allenyl Sulfones to Access Chiral Allylic Sulfones DOI

Peidong Sun,

Xiaomei Kong,

Huang Jing-wen

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 14, 2025

An efficient method for copper-catalyzed asymmetric protoboration of allenyl sulfones with bis(pinacolato)diboron was developed, providing chiral allylic high efficiency and excellent enantioselectivity. Notably, the directing effect sulfone group plays a pivotal role in achieving both regioselectivity

Language: Английский

Citations

1
N-Sulfonylation of azoles with sulfonyl hydrazides enabled by electrocatalysis DOI
Cheng Huang, Kang Chen, Zhihong Liu

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(15), P. 8706 - 8710

Published: Jan. 1, 2024

We report an electrochemical strategy for N -sulfonylation of azoles with sulfonyl hydrazides via radical–radical cross-coupling.

Language: Английский

Citations

5
Unraveling the Potential of Vinyl Ether as an Ethylene Surrogate in Heteroarene C─H Functionalization via the Spin‐Center Shift DOI Creative Commons
Wonjun Choi,

Leejae Kim,

Sungwoo Hong

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(19)

Published: March 13, 2024

Abstract Despite the simplicity and abundance of ethylene, its practical application presents significant hurdles due to nature as a highly flammable gas. Herein, strategic use easily handled vinyl ether is reported latent ethylene surrogate achieved via spin‐center shift (SCS) pathway, enabling successful three‐component reaction that bridges heteroarenes various coupling partners, including sulfinates, thiols, phosphine oxides. Through photoredox catalytic process, α ‐oxy radicals are generated by combining with phenyl ether, which subsequently added N‐heteroarenes. Subsequently, radical‐mediated SCS pathway serves driving force for C─O bond cleavage, effectively engaging phenoxy group leaving group. In addition, broadening utility method, valuable synthon provided efficient C─H vinylation N‐heteroarenes following sulfonyl elimination. This approach not only enriches toolbox synthetic methodology but also provides more streamlined alternative, circumventing challenges associated direct gas usage. The versatility particularly evident in late‐stage functionalizations medicinally relevant molecules peptides, underscores capability produce invaluable compounds vinylated N‐heteroarene derivatives.

Language: Английский

Citations

4
Harnessing the potential of acyl triazoles in bifunctional cobalt-catalyzed radical cross-coupling reactions DOI Creative Commons
Chang‐Yin Tan, Sungwoo Hong

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 13, 2024

Persistent radicals facilitate numerous selective radical coupling reactions. Here, we have identified acyl triazole as a new and versatile moiety for generating persistent intermediates through single-electron transfer processes. The efficient generation of these is facilitated by the formation substrate-coordinated cobalt complexes, which subsequently engage in cross-coupling Remarkably, triazole-coordinated complexes exhibit metal-hydride hydrogen atom (MHAT) capabilities with alkenes, enabling synthesis diverse ketone products without need external ligands. By leveraging effect, this catalytic approach also allows development other reactions two representative precursors. discovery triazoles effective substrates ligands catalysis, combined bifunctional nature system, opens up avenues design sustainable organic transformations. radical-mediated has emerged powerful tool forging C–C bonds. authors identify processes, context cobalt-catalysed carbon-carbon couplings under photoirradiation.

Language: Английский

Citations

4
Catalyst‐Free Visible Light‐Driven Hydrosulfonylation of Alkenes and Alkynes with Sulfonyl Chlorides in Water DOI

Xi‐Rui Xia,

Juan Du, Yuxing Zhang

et al.

ChemSusChem, Journal Year: 2024, Volume and Issue: unknown

Published: June 8, 2024

Abstract A convenient and sustainable method for synthesizing sulfonyl‐containing compounds through a catalyst‐free aqueous‐phase hydrosulfonylation of alkenes alkynes with sulfonyl chlorides under visible light irradiation is presented. Unactivated alkenes, electron‐deficient alkyl aryl can be hydrosulfonylated various at room temperature excellent yields geometric selectivities by using tris(trimethylsilyl)silane as hydrogen atom donor silyl radical precursor to activate chlorides. Mechanistic studies revealed that the photolysis in aqueous solution produce crucial success this reaction.

Language: Английский

Citations

3
Recent Advances in Strategies for Halide Atom Transfer (XAT) and Their Applications DOI

Yifeng Jiang,

Yanli Yin, Zhiyong Jiang

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(6), P. 1733 - 1733

Published: Jan. 1, 2024

Language: Английский

Citations

3
Electrochemical Synthesis of Vinyl, Alkyl, and Allyl Sulfones from Sodium Sulfinates and Olefins DOI

Pengkai Fang,

Qingxu Wang,

Xiaoqian Shen

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12619 - 12627

Published: Aug. 16, 2024

An electrochemical synthesis of vinyl, alkyl, and allyl sulfones using sodium sulfinates olefins was reported. This method uses direct current to pass through an undivided cell equipped with graphite carbon electrodes, a series diverse sulfone compounds can be synthesized at room temperature in high yields.

Language: Английский

Citations

3