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[2+3]-Cycloadditions of Phosphonodithioformate S-Methanides with C=S, N=N, and C=C Dipolarophiles


Mloston, Grzegorz; Urbaniak, Katarzyna; Gulea, Mihaela; Masson, Serge; Linden, Anthony; Heimgartner, Heinz (2005). [2+3]-Cycloadditions of Phosphonodithioformate S-Methanides with C=S, N=N, and C=C Dipolarophiles. Helvetica Chimica Acta, 88(10):2582-2592.

Abstract

The reaction of the methyl (dialkoxyphosphinyl)-dithioformates (= methyl dialkoxyphosphinecarbodithioate 1-oxides) 10 with CH2N2 at − 65° in THF yielded cycloadducts which eliminated N2 between − 40 and − 35° to give the corresponding phosphonodithioformate S-methanides ( =methylenesulfonium (dialkoxyoxidophosphino)(methylthio)methylides) 11 (Scheme 3). These reactive 1,3-dipoles were intercepted by aromatic thioketones to yield 1,3-dithiolanes. Whereas the reaction with thiobenzophenone (12b) led to the sterically more congested isomers 15 regioselectively, a mixture of both regioisomers was obtained with 9H-fluorene-9-thione (12a). Trapping of 11 with phosphono- and sulfonodithioformates led exclusively to the sterically less hindered 1,3-dithiolanes 16 and 18, respectively (Scheme 4). In addition, reactive C[DOUBLE BOND]C dipolarophiles such as ethenetetracarbonitrile, maleic anhydride, and N-phenylmaleimide as well as the N[DOUBLE BOND]N dipolarophile dimethyl diazenedicarboxylate were shown to be efficient interceptors of 11 (Scheme 5).

Abstract

The reaction of the methyl (dialkoxyphosphinyl)-dithioformates (= methyl dialkoxyphosphinecarbodithioate 1-oxides) 10 with CH2N2 at − 65° in THF yielded cycloadducts which eliminated N2 between − 40 and − 35° to give the corresponding phosphonodithioformate S-methanides ( =methylenesulfonium (dialkoxyoxidophosphino)(methylthio)methylides) 11 (Scheme 3). These reactive 1,3-dipoles were intercepted by aromatic thioketones to yield 1,3-dithiolanes. Whereas the reaction with thiobenzophenone (12b) led to the sterically more congested isomers 15 regioselectively, a mixture of both regioisomers was obtained with 9H-fluorene-9-thione (12a). Trapping of 11 with phosphono- and sulfonodithioformates led exclusively to the sterically less hindered 1,3-dithiolanes 16 and 18, respectively (Scheme 4). In addition, reactive C[DOUBLE BOND]C dipolarophiles such as ethenetetracarbonitrile, maleic anhydride, and N-phenylmaleimide as well as the N[DOUBLE BOND]N dipolarophile dimethyl diazenedicarboxylate were shown to be efficient interceptors of 11 (Scheme 5).

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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
Uncontrolled Keywords:Physical and Theoretical Chemistry, Inorganic Chemistry, Organic Chemistry, Biochemistry, Drug Discovery, Catalysis
Language:English
Date:2005
Deposited On:27 Mar 2013 08:29
Last Modified:18 Aug 2018 06:43
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Polish State Committee for Scientific Research, Swiss National Science Foundation, F. Hoffmann-La Roche AG, Basel
OA Status:Green
Publisher DOI:https://doi.org/10.1002/hlca.200590198
Project Information:
  • : Funder
  • : Grant ID
  • : Project TitlePolish State Committee for Scientific Research
  • : FunderSNSF
  • : Grant ID
  • : Project TitleSwiss National Science Foundation
  • : Funder
  • : Grant ID
  • : Project TitleF. Hoffmann-La Roche AG, Basel

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