71899-75-7Relevant articles and documents
Chemoenzymatic Oxosulfonylation-Bioreduction Sequence for the Stereoselective Synthesis of β-Hydroxy Sulfones
González-Sabín, Javier,Gotor-Fernández, Vicente,López-Agudo, Marina,Lavandera, Iván,Ríos-Lombardía, Nicolás
, (2021/08/23)
A series of optically active β-hydroxy sulfones has been obtained through an oxosulfonylation-stereoselective reduction sequence in aqueous medium. Firstly, β-keto sulfones were synthesized from arylacetylenes and sodium sulfinates to subsequently develop the carbonyl reduction in a highly selective fashion using alcohol dehydrogenases as biocatalysts. Optimization of the chemical oxosulfonylation reaction was investigated, finding inexpensive iron(III) chloride hexahydrate (FeCl3 ? 6H2O) as the catalyst of choice. The selection of isopropanol in the alcohol-water media resulted in high compatibility with the enzymatic process for enzyme cofactor recycling purposes, providing a straightforward access to both (R)- and (S)-β-hydroxy sulfones. The practical usefulness of this transformation was illustrated by describing the synthesis of a chiral intermediate of Apremilast. Interestingly, the development of a chemoenzymatic cascade approach avoided the isolation of β-keto sulfone intermediates, which allowed the preparation of chiral β-hydroxy sulfones in high conversion values (83–94 %) and excellent optical purities (94 to >99 % ee).
Dioxygen-Triggered Oxosulfonylation/Sulfonylation of Terminal Olefins toward β-Keto Sulfones/Sulfones
Wang, Yanjie,Zhao, Yuhan,Cai, Changqun,Wang, Lingyun,Gong, Hang
, p. 8296 - 8301 (2021/11/13)
A dioxygen-triggered oxosulfonylation/sulfonylation of unactivated olefins to achieve β-keto sulfones/sulfones has been developed. Interestingly, pluralistic mechanisms were found when different types of compounds were applied as substrates, and different products were achieved. The reaction is carried out with a high atomic efficiency in the absence of a metal and a catalyst at room temperature under an air atmosphere. Importantly, as a proof-of-concept, a bioactive molecule was synthesized on a gram-scale level using this method.
Copper-Catalyzed Aerobic Oxidative Cleavage of Unstrained Carbon-Carbon Bonds of 1,1-Disubstituted Alkenes with Sulfonyl Hydrazides
Yi, Dong,He, Linying,Qi, Zhongyu,Zhang, Zhijie,Li, Mengshun,Lu, Ji,Wei, Jun,Du, Xi,Fu, Qiang,Wei, Siping
, p. 859 - 865 (2021/03/04)
Alkoxy radical-mediated carbon-carbon bond cleavages have emerged as a powerful strategy to complement traditional ionic-type transformations. However, carbon-carbon cleavage reaction triggered by alkoxy radical intermediate derived from the combination of alkyl radical and dioxygen, is scarce and underdeveloped. Herein, we report alkoxy radical, which was generated from alkyl radical and dioxygen, mediated selective cleavage of unstrained carbon-carbon bond for the oxysulfonylation of 1,1-disubstituted alkenes, providing facile access to a variety of valuable β-keto sulfones. Mechanistic experiments indicated alkoxy radical intermediate that underwent subsequent regioselective β-scission might be involved in the reaction and preliminary computational studies were conducted to provide a detailed explanation on the regioselectivity of the C—C bond cleavage. Notably, the strategy was successfully applied for constructing uneasily obtained architecturally intriguing molecules.
