Regioselectivity in the Ring Opening of Epoxides: A Metal-Free Cascade 
C–S/C–O Bond Formation Approach to 1,3-Oxathiolan-2-ylidenes through Heteroannulation of α-Enolic Dithioesters at Room Temperature

Gaurav Shukla; Anugula Nagaraju; Abhijeet Srivastava; Girijesh Kumar Verma; Keshav Raghuvanshi; Maya Shankar Singh

doi:10.1055/s-0033-1341086

Synthesis, Inhaltsverzeichnis

Synthesis 2014; 46(13): 1815-1822
DOI: 10.1055/s-0033-1341086

paper

Regioselectivity in the Ring Opening of Epoxides: A Metal-Free Cascade C–S/C–O Bond Formation Approach to 1,3-Oxathiolan-2-ylidenes through Heteroannulation of α-Enolic Dithioesters at Room Temperature

Autoren

Gaurav Shukla

^aDepartment of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi-221005, India Fax: +91(542)2368127 eMail: mssinghbhu@yahoo.co.in
Anugula Nagaraju

^aDepartment of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi-221005, India Fax: +91(542)2368127 eMail: mssinghbhu@yahoo.co.in
Abhijeet Srivastava

^aDepartment of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi-221005, India Fax: +91(542)2368127 eMail: mssinghbhu@yahoo.co.in
Girijesh Kumar Verma

^aDepartment of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi-221005, India Fax: +91(542)2368127 eMail: mssinghbhu@yahoo.co.in
Keshav Raghuvanshi

^bInstitute für Organische und Biomolekulare Chemie, Georg-August-Universität, Tammannstrasse 2, 37077 Göttingen, Germany
Maya Shankar Singh*

^aDepartment of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi-221005, India Fax: +91(542)2368127 eMail: mssinghbhu@yahoo.co.in

Abstract

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Abstract

An operationally simple and efficient approach to hitherto unreported and synthetically demanding 1,3-oxathiolan-2-ylidenes has been developed. The approach involves a cascade [2+3] heteroannulation of α-enolic dithioesters with epoxides promoted by non-nucleophilic moderate base Cs₂CO₃ at room temperature. Typical features of this strategy include metal-free mild reaction conditions, atom-economy, high yields, and efficacy of forming two consecutive C–S and C–O bonds, and one ring in a single stroke. MeSH is the only by-product, and the stereochemistry of the exocyclic α-oxoketene moiety of 1,3-oxathiolane was assigned to have Z-configuration.

Key words

epoxides - oxathiolanes - heteroannulation - metal-free conditions - regioselective - cascade reaction

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Referenzen

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Recent papers:

13a Verma RK, Verma GK, Shukla G, Nagaraju A, Singh MS. ACS Comb. Sci. 2012; 14: 224
13b Nandi GC, Ila H, Junjappa H, Singh MS. Eur. J. Org. Chem. 2012; 967
13c Nagaraju A, Verma GK, Shukla G, Verma RK, Srivastava A, Raghuvanshi K, Singh MS. Green Chem. 2013; 15: 954
13d Shukla G, Verma GK, Nagaraju A, Verma RK, Raghuvanshi K, Singh MS. RSC Adv. 2013; 3: 13811
13e Chowdhury S, Chanda T, Koley S, Ramulu BJ, Jones RC. F, Singh MS. Org. Lett. 2013; 15: 5386
13f Koley S, Chowdhury S, Chanda T, Ramulu BJ, Singh MS. Tetrahedron 2013; 69: 8013
13g Samai S, Chanda T, Ila H, Singh MS. Eur. J. Org. Chem. 2013; 4026
13h Chowdhury S, Chanda T, Koley S, Ramulu BJ, Raghuvanshi K, Singh MS. Tetrahedron 2014; 70: 914

14 CCDC 981652 (3e), CCDC 981650 (3r) and CCDC 981651 (A). Crystallographic data for these compounds can be obtained free of charge from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44(1223)336033; E-mail: deposit@ccdc.cam.ac.uk.

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