Copper-mediated C-H activation/C-S cross-coupling of heterocycles with thiols

Handle URI:
http://hdl.handle.net/10754/561915
Title:
Copper-mediated C-H activation/C-S cross-coupling of heterocycles with thiols
Authors:
Ranjit, Sadananda; Lee, Richmond; Heryadi, Dodi; Shen, Chao; Wu, Jien; Zhang, Pengfei; Huang, Kuo-Wei ( 0000-0003-1900-2658 ) ; Liu, Xiaogang
Abstract:
We report the synthesis of a series of aryl- or alkyl-substituted 2-mercaptobenzothiazoles by direct thiolation of benzothiazoles with aryl or alkyl thiols via copper-mediated aerobic C-H bond activation in the presence of stoichiometric CuI, 2,2′-bipyridine and Na 2CO 3. We also show that the approach can be extended to thiazole, benzimidazole, and indole substrates. In addition, we present detailed mechanistic investigations on the Cu(I)-mediated direct thiolation reactions. Both computational studies and experimental results reveal that the copper-thiolate complex [(L)Cu(SR)] (L: nitrogen-based bidentate ligand such as 2,2′-bipyridine; R: aryl or alkyl group) is the first reactive intermediate responsible for the observed organic transformation. Furthermore, our computational studies suggest a stepwise reaction mechanism based on a hydrogen atom abstraction pathway, which is more energetically feasible than many other possible pathways including β-hydride elimination, single electron transfer, hydrogen atom transfer, oxidative addition/reductive elimination, and σ-bond metathesis. © 2011 American Chemical Society.
KAUST Department:
KAUST Catalysis Center (KCC); Biological and Environmental Sciences and Engineering (BESE) Division; Core Labs; Chemical Science Program; Physical Sciences and Engineering (PSE) Division; HCL
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Organic Chemistry
Issue Date:
4-Nov-2011
DOI:
10.1021/jo2017444
PubMed ID:
21958157
Type:
Article
ISSN:
00223263
Sponsors:
This study was supported in part by the Ministry of Education (MOE2010-T2-083), the Singapore Peking Oxford Research Enterprise (SPORE), the Science and Technology Plan of Zhejiang Province (2011C24004), and the Singapore-MIT alliance. X.L. is grateful to the National University of Singapore for the Young Research Award (C-143-000-022). R.L., D.H., and K.-W.H. are grateful for funding from KAUST and computing time from the NOOR computer cluster managed by the KAUST supercomputing team.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Biological and Environmental Sciences and Engineering (BESE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorRanjit, Sadanandaen
dc.contributor.authorLee, Richmonden
dc.contributor.authorHeryadi, Dodien
dc.contributor.authorShen, Chaoen
dc.contributor.authorWu, Jienen
dc.contributor.authorZhang, Pengfeien
dc.contributor.authorHuang, Kuo-Weien
dc.contributor.authorLiu, Xiaogangen
dc.date.accessioned2015-08-03T09:34:01Zen
dc.date.available2015-08-03T09:34:01Zen
dc.date.issued2011-11-04en
dc.identifier.issn00223263en
dc.identifier.pmid21958157en
dc.identifier.doi10.1021/jo2017444en
dc.identifier.urihttp://hdl.handle.net/10754/561915en
dc.description.abstractWe report the synthesis of a series of aryl- or alkyl-substituted 2-mercaptobenzothiazoles by direct thiolation of benzothiazoles with aryl or alkyl thiols via copper-mediated aerobic C-H bond activation in the presence of stoichiometric CuI, 2,2′-bipyridine and Na 2CO 3. We also show that the approach can be extended to thiazole, benzimidazole, and indole substrates. In addition, we present detailed mechanistic investigations on the Cu(I)-mediated direct thiolation reactions. Both computational studies and experimental results reveal that the copper-thiolate complex [(L)Cu(SR)] (L: nitrogen-based bidentate ligand such as 2,2′-bipyridine; R: aryl or alkyl group) is the first reactive intermediate responsible for the observed organic transformation. Furthermore, our computational studies suggest a stepwise reaction mechanism based on a hydrogen atom abstraction pathway, which is more energetically feasible than many other possible pathways including β-hydride elimination, single electron transfer, hydrogen atom transfer, oxidative addition/reductive elimination, and σ-bond metathesis. © 2011 American Chemical Society.en
dc.description.sponsorshipThis study was supported in part by the Ministry of Education (MOE2010-T2-083), the Singapore Peking Oxford Research Enterprise (SPORE), the Science and Technology Plan of Zhejiang Province (2011C24004), and the Singapore-MIT alliance. X.L. is grateful to the National University of Singapore for the Young Research Award (C-143-000-022). R.L., D.H., and K.-W.H. are grateful for funding from KAUST and computing time from the NOOR computer cluster managed by the KAUST supercomputing team.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleCopper-mediated C-H activation/C-S cross-coupling of heterocycles with thiolsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Divisionen
dc.contributor.departmentCore Labsen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentHCLen
dc.identifier.journalThe Journal of Organic Chemistryen
dc.contributor.institutionDepartment of Chemistry, National University of Singapore, Singapore 117543, Singaporeen
dc.contributor.institutionInstitute of Materials Research and Engineering, A STAR, 3 Research Link, Singapore 117602, Singaporeen
dc.contributor.institutionCollege of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036, Chinaen
kaust.authorLee, Richmonden
kaust.authorHeryadi, Dodien
kaust.authorHuang, Kuo-Weien
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