{"title":"Asymmetric Radical-Type 1,2-Alkoxy-Sulfenylation of Benzoxazole-2-Thiols to Vinylarenes Catalyzed by Chiral Vanadyl Complexes","authors":"Yueh-Hua Liu, Hao-Yang Tsui, Pei-Hsuan Chien, Chien-Tien Chen","doi":"10.1021/acscatal.4c02460","DOIUrl":null,"url":null,"abstract":"Chiral vanadyl complex derived from <i>N</i>-salicylidene-<i>tert</i>-butyl-<span>l</span>-glycinate bearing a 3-(2,5-dimethyl)phenyl-5-bromo substituent was first tested for the catalytic feasibility of asymmetric intermolecular 1,2-alkoxy-sulfenylation of styrene with three different types of six- and five-membered ring heteroaromatic thiols in the presence of <i>t</i>-butyl hydroperoxide in methanol at ambient temperature. Among them, 2-mercapto-benzoxazole (BzOxz-SH) was identified as the best candidate. A variety of chiral vanadyl complexes bearing 3-aryl-5-bromo, 3,5-dihalo-, and benzo-fused salicylidene templates were further examined for optimizing yields and enantio-control. The best scenario involved the use of 5 mol % 3,5-dibromo or -dichloro catalyst at 0 °C with BzOxz-SH in MeOH. The asymmetric catalytic cross-coupling reactions proceeded smoothly with enantioselectivities of up to 94% ee of (<i>R</i>)-configuration by using the 3,5-dichloro catalyst for various 1° alcohols by screening through various 4-, 3-, 3,4-, 3,5-, and 2-substituted (including Me/<i>t</i>-Bu, Ph, OR, Cl/Br, OAc, NO<sub>2</sub>, C(O)Me, CO<sub>2</sub>Me, CN, and benzo-fused) vinylarenes. Further improvement to 96% ee was achieved by the use of 5-methyl-BzOxz-SH. The origin and catalytic mechanism of enantiocontrol through homolytic methoxy delivery to incipient benzylic radical intermediates by vanadyl-bound methoxide were proposed.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3000,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acscatal.4c02460","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Chiral vanadyl complex derived from N-salicylidene-tert-butyl-l-glycinate bearing a 3-(2,5-dimethyl)phenyl-5-bromo substituent was first tested for the catalytic feasibility of asymmetric intermolecular 1,2-alkoxy-sulfenylation of styrene with three different types of six- and five-membered ring heteroaromatic thiols in the presence of t-butyl hydroperoxide in methanol at ambient temperature. Among them, 2-mercapto-benzoxazole (BzOxz-SH) was identified as the best candidate. A variety of chiral vanadyl complexes bearing 3-aryl-5-bromo, 3,5-dihalo-, and benzo-fused salicylidene templates were further examined for optimizing yields and enantio-control. The best scenario involved the use of 5 mol % 3,5-dibromo or -dichloro catalyst at 0 °C with BzOxz-SH in MeOH. The asymmetric catalytic cross-coupling reactions proceeded smoothly with enantioselectivities of up to 94% ee of (R)-configuration by using the 3,5-dichloro catalyst for various 1° alcohols by screening through various 4-, 3-, 3,4-, 3,5-, and 2-substituted (including Me/t-Bu, Ph, OR, Cl/Br, OAc, NO2, C(O)Me, CO2Me, CN, and benzo-fused) vinylarenes. Further improvement to 96% ee was achieved by the use of 5-methyl-BzOxz-SH. The origin and catalytic mechanism of enantiocontrol through homolytic methoxy delivery to incipient benzylic radical intermediates by vanadyl-bound methoxide were proposed.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.