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Hetero-Diels-Alder Reactions of α-Nitrosoalkenes with Ferrocenyl, Hetaryl and Cycloaliphatic Thioketones


Mloston, Grzegorz; Urbaniak, Katarzyna; Zimmer, Reinhol; Reissig, Hans-Ulrich; Heimgartner, Heinz (2018). Hetero-Diels-Alder Reactions of α-Nitrosoalkenes with Ferrocenyl, Hetaryl and Cycloaliphatic Thioketones. ChemistrySelect, 3:11724-11728.

Abstract

The in situ generated α-nitrosoalkenes react with ferrocenyl, hetaryl and cycloaliphatic thioketones yielding 4H-1,5,2-oxa- thiazines as products of the hetero-Diels-Alder reaction. These products are formed in a perfect regioselective manner. A similar reactivity is displayed by a thiochalcone (1,3-diphenylprop-2-ene-1-thione), and in that case, the [4 + 2]-cyclo-addition occurs also chemoselectively and regioselectively along the C=S bond acting as a heterodienophile. The stability of the 4H-1,5,2-oxathiazines depends on the type of substituents, and in the case of ferrocenyl thioketones, the diferrocenyl representative is the reagent of choice. The replacement of one ferrocenyl group by an ethyl group leads to a dramatic decrease of the product stability. Sterically crowded cycloaliphatic thioketones derived from 2,2,4,4-tetramethylcyclobutane-1,3-dione are exceptional dienophiles in reactions with trifluoromethyl-substituted nitrosoalkenes, and in these cases, a remarkably stable 3-trifluoromethyl-4H-1,5,2-oxathiazine derivative was obtained. For the first time, perfectly stable and non-odorous 2,2,4,4- tetramethylcyclobutane-1,3-dithione was explored as an active heterodienophile for a two-fold hetero-Diels-Alder reaction.

Abstract

The in situ generated α-nitrosoalkenes react with ferrocenyl, hetaryl and cycloaliphatic thioketones yielding 4H-1,5,2-oxa- thiazines as products of the hetero-Diels-Alder reaction. These products are formed in a perfect regioselective manner. A similar reactivity is displayed by a thiochalcone (1,3-diphenylprop-2-ene-1-thione), and in that case, the [4 + 2]-cyclo-addition occurs also chemoselectively and regioselectively along the C=S bond acting as a heterodienophile. The stability of the 4H-1,5,2-oxathiazines depends on the type of substituents, and in the case of ferrocenyl thioketones, the diferrocenyl representative is the reagent of choice. The replacement of one ferrocenyl group by an ethyl group leads to a dramatic decrease of the product stability. Sterically crowded cycloaliphatic thioketones derived from 2,2,4,4-tetramethylcyclobutane-1,3-dione are exceptional dienophiles in reactions with trifluoromethyl-substituted nitrosoalkenes, and in these cases, a remarkably stable 3-trifluoromethyl-4H-1,5,2-oxathiazine derivative was obtained. For the first time, perfectly stable and non-odorous 2,2,4,4- tetramethylcyclobutane-1,3-dithione was explored as an active heterodienophile for a two-fold hetero-Diels-Alder reaction.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:November 2018
Deposited On:22 Nov 2018 14:40
Last Modified:09 Dec 2018 06:48
Publisher:Wiley-VCH Verlag
ISSN:2365-6549
OA Status:Closed
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1002/slct.201803096
Project Information:
  • : FunderRector of the University of Lodz
  • : Grant ID
  • : Project Title

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