Alkyl Sulfonyl Fluorides as Ambiphiles in the Stereoselective, Palladium(II)-Catalyzed Cyclopropanation of Unactivated Alkenes

• DOI: 10.26434/chemrxiv-2024-pdplt
• Publication Date: 2024-11-13T10:41:08Z
• Authors: Yilin Cao; Warabhorn Rodphon; Turki Alturaifi; Al Lisboa; Zhouyang Ren; Job Struijs; Hui-Qi Ni; Taras Savchuk; Pavel Mykhailiuk; Richard Loach; Shouliang Yang; Indrawan McAlpine; Donna Blackmond; Peng Liu; K. Barry Sharpless; Keary Engle
• Keywords: Sulfonyl

The ambiphilic reactivity of alkyl sulfonyl fluorides in the stereoselective synthesis diverse cyclopropanes from ole-fins under palladium(II) catalysis is presented. fluoride functionality serves as both an acidifying group and internal oxidant within ambiphile, enabling successive carbopalladation oxidative addition steps catalytic cycle, respectively. transformation grants access to cis-substituted exhibits broad compatibility with various fluorides, including those bearing –CN, –CO2R, isoxazolyl, pyrazolyl, aryl groups. With alkene substrates, 1,2-3-trisubstituted that are otherwise challenging synthesize formed good moderate yield predictable diastereoselectivity. Detailed mechanistic insights reaction progress kinetic analysis (RPKA) density functional theory (DFT) calculations reveal SN2-type C–SO2F turnover-limiting diastereoselectivity-determining step.