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

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

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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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Recent papers:

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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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