Catalytic Enantioselective Intermolecular Three-Component Sulfenylative Difunctionalizations of 1,3-Dienes

Abstract

This work demonstrates regio- and enantioselective intermolecular three-component oxysulfenylations of 1,3-dienes with alcohols, phenols, acids, and water as O-nucleophiles. These reactions were enabled by the cooperative catalysis of chiral sulfide and phosphoric acid. Various useful sulfur-containing allylic ethers, allylic esters, and allylic alcohols were readily obtained in moderate to excellent yields with high to excellent enantioselectivities and excellent regioselectivities. This protocol provides high chemo-, regio-, and enantioselectivities together with a broad scope and good functional group compatibility.

Asymmetric Radical-Type 1,2-Alkoxy-Sulfenylation of Benzoxazole-2-Thiols to Vinylarenes Catalyzed by Chiral Vanadyl Complexes

“…10 Subsequent remarkable extension to intermolecular versions using 2,2′binol-derived chiral phosphoric acid 11,12 cocatalysts by Prof. Zhi-Min Chen and co-workers with alcohols and phenols as the nucleophiles led to the successful enantioselective synthesis of 1,2-alkoxy/phenoxy-arenethiols (Scheme 1B-2). 13,14 Alternatively, remarkable uses of chiral 1-N-acyl/sulfonylamino-2arylthio/seleno indanes and (thio)ureas for in situ chiral thiosulfonium ion formation have also been demonstrated with significant breakthroughs (Scheme 1B-3). 15−18 Subsequently, a diverse array of C-, O-, and N-centered nucleophiles can thus be utilized for various applications.…”

Copper-Catalyzed 1,2-Sulfonyletherification of 1,3-Dienes

“…On the basis of control experiments and the literature, a possible catalytic cycle for the regioselective 1,2-sulfone etherification is presented in Figure . , Originally, this difunctionalization is triggered by single-electron transfer (SET) of sulfonyl chlorides 2a with Cu­(I), with concomitant generation of sulfonyl radical A and the Cu­(II) halide complex. , Subsequently, the intermolecular regioselective addition of sulfonyl radical A to phenyl butadiene 1a affords the critical and relatively stabilized allyl carbon radical B . Radical intermediate B is oxidized by the Cu­(II) halide complex to access cation intermediate C or further to afford unstable allyl-chlorinated product 4aaa′ .…”

Atroposelective Sulfenylation of Biaryl Anilines Catalyzed by Chiral SPINOL-Derived Selenide

“…Catalytic enantioselective electrophilic sulfenylation of arene derivatives is a direct and efficient method for the construction of axially chiral organosulfur compounds. However, compared with the well-developed methods for catalytic asymmetric electrophilic sulfenylation of alkenes, − catalytic enantioselective electrophilic sulfenylation of arene derivatives is still a challenge. , Thus, we aimed to develop methods for the catalytic atroposelective desymmetrization of symmetric biaryl anilines via electrophilic sulfenylation, which could be used to construct axially chiral sulfur-containing biaryl aniline compounds (Scheme c). Herein, we report the design and synthesis of a new chiral 6,6′-dianisole substituted 1,1′-spirobiindane-7,7′-diol (SPINOL)-derived selenide catalyst that allows for the atroposelective sulfenylation of biaryl aniline compounds (Scheme c).…”