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Thia-Diels–Alder reactions of hetaryl thioketones with nonactivated 1,3-dienes leading to 3,6-dihydro-2H-pyrans: evidence for a diradical mechanism

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Chemistry of Heterocyclic Compounds Aims and scope

A Correction to this article was published on 01 May 2021

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Dihetaryl thioketones possessing thiophen-2-yl and selenophen-2-yl rings react as “superdienophilic” reagents with nonactivated 1,3-dienes such as 2,3-dimethylbuta-1,3-diene, cyclopentadiene, and mixtures of isomeric hexa-2,4-dienes to produce the expected 2H-thiopyrans in moderate to excellent yields. In the latter case, the corresponding cis-2,2-dihetaryl-3,6-dimethyl-3,6-dihydro-2H-thiopyrans are formed as the sole products in a stereoconvergent thia-Diels–Alder reaction. A stepwise mechanism via delocalized diradical intermediates is postulated to rationalize the observed reaction course. Treatment of 4,5-dimethyl-2,2-di(thiophen-2-yl)-3,6-dihydro-2H-thiopyran with excess of m-CPBA at room temperature leads to the oxidation of the C=C bond and the sulfur atom in the six-membered ring.

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The authors thank the National Science Center (Cracow, PL) for financial support within the project Maestro (Grant Number: Dec-2012/06/A/ST5/00219). This work is a part of the planned PhD thesis of Paulina Grzelak, University of Łódź.

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Authors and Affiliations

  1. Department of Organic and Applied Chemistry, University of Łódź, 12 Tamka, Łódź, PL-91-403, Poland

    Grzegorz Mlostoń & Paulina Grzelak

  2. Department of Chemistry, University of Zurich, 190 Winterthurerstrasse, Zurich, CH-8057, Switzerland

    Anthony Linden & Heinz Heimgartner

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  1. Grzegorz Mlostoń
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  2. Paulina Grzelak
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Correspondence to Grzegorz Mlostoń.

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Published in Khimiya Geterotsiklicheskikh Soedinenii, 2017, 53(5), 518–525

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Mlostoń, G., Grzelak, P., Linden, A. et al. Thia-Diels–Alder reactions of hetaryl thioketones with nonactivated 1,3-dienes leading to 3,6-dihydro-2H-pyrans: evidence for a diradical mechanism. Chem Heterocycl Comp 53, 518–525 (2017). https://doi.org/10.1007/s10593-017-2086-9

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