Phenanthroline-Initiated Anti-selective Hydrosulfonylation of Unactivated Alkynes with Sulfonyl Chlorides

Abstract

A simple and general method for anti-selective hydrosulfonylation of unactivated alkynes with sulfonyl chlorides in the presence of a catalytic amount of phenanthroline-based Lewis base and (Me 3 Si) 3 SiH as the hydrogen atom donor has been developed. The protocol proceeds efficiently under mild and metal-free conditions, delivering a diverse set of (Z)-vinyl sulfones with high stereoselectivity. Additionally, the method displays excellent functional-group compatibility and can be applied to the late-stage modifications of complex drugs and their derivatives. Experimental and density functional theory studies unveiled that the key to the transformation's success is the employment of a phenanthroline-based Lewis base, which interacts with sulfonyl chlorides to form a halogen-bond complex that accelerates the cleavage of the S−Cl bonds of sulfonyl chlorides under the irradiation of visible light.

Nickel-Catalyzed Reaction between Vinyl Azides and an Alkyl Sulfonyl Radical Generated from DMSO: Rapid Access to β-Keto Sulfones

“…Alkyl sulfonyl fragments widely exist in molecules with anticancer and anti-inflammatory activities, as well as antibacterial activities, displaying a significant synthetic value. − An important approach for the construction of this skeleton is the involvement of alkyl sulfonyl radicals. − In this case, the source of alkyl sulfonyl radicals commonly comprises three ways (Scheme A): (1) Direct generation of alkyl sulfonyl radicals from alkyl sulfonyl compounds (such as sulfonic acid, sodium sulfonate, sulfonyl hydrazine, sulfonyl chloride, selenosulfonates, etc. ); − (2) Formation of carbon radicals by homolytic cleavage of C–Y (Y = X, C, B, N, S) bonds, which then combine with SO 2 sources to produce alkyl sulfonyl radicals; − (3) Production of carbon radicals through ring-opening of small-ring compounds, followed by in situ capture of SO 2 sources to afford the corresponding alkyl sulfonyl radicals. − Nevertheless, these methods generally require prefunctionalization or pregeneration of carbon radicals.…”

Hydrosulfonylation of Alkynes for Stereodivergent Synthesis of Vinyl Sulfones: Synthetic Strategy and Mechanistic Insights

“…Notably, Gouverneur et al developed a visible light-mediated hydrosulfonylation of alkenes and alkyl-substituted alkynes using an iridium-based photocatalyst (Scheme B-1) . Recently, Qu and Zhang developed an efficient pathway for the synthesis of ( Z )-vinyl sulfones using alkyl-substituted alkynes and sulfonyl chlorides in the presence of organic photocatalysts (Scheme B-2) . This study allowed for an extensive exploration of the substrate scope, starting with alkyl-substituted alkynes, providing valuable insights into the underlying process.…”

Regio- and stereoselective manganese-catalyzed hydrosulfonylation of alkynes: facile access to Z-vinyl sulfones

“…12 To ameliorate this deficiency, developing a more efficient and environmentally benign synergistic methodology to accomplish the synthesis of ( Z )-vinyl sulfones with highly controllable stereoselectivity is highly desirable and urgently needed. 13…”