C‐Phosphorylated N‐(Trichloroethylidene)sulfonamides: A New Type of Highly Electrophilic Imines

Abstract

A convenient preparative approach to previously unknown, highly electrophilic C‐phosphorylated N‐arylsulfonylimines 1, based on fairly readily accessible α‐phosphorylated sulfonamides 5, has been developed. Compounds 1 react with trialkyl phosphites or ethyl diphenylphosphinite in the aza‐Perkow reaction scheme to give C,N‐diphosphorylated N‐dichlorovinylsulfonamides 8. On treatment with O‐ and S‐nucleophilic agents (alcohols, thiols, thiophenols), 1 forms addition products 12 and 15, the functionalized derivatives of α‐aminophosphonic acids, while interaction between 1 and mercaptoacetic acid proceeds with intramolecular cyclization of the intermediate adduct to produce the novel 2‐phosphorylated thiazolidinones 17. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Chemistry of heterocyclic compounds at the Institute of Organic Chemistry, National Academy of Sciences of Ukraine (Review)

“…The cyclization of imines with -mercaptocarboxylic acids at the C=N bond opens up the way to derivatives of thiazolidones with a phosphoryl group [121][122][123][124]. Syntheses of the functionalized heterodienes used in the production of five-and six-membered heterocycles as a result of [4+1] and [4+2] cycloaddition reactions were realized.…”

Synthesis of N-[1-(1H-Benzimidazol-2-ylsulfanyl)-2,2,2-trichloroethyl]arenesulfonamides by Reaction of N-(2,2,2-Trichloroethylidene)arenesulfonamides with 1H-benzimidazole-2-thiol

“…However, only a few examples of analogous reactions with sulfur-centered nucleophiles were reported; in particular, addition of phenylmethanethiol, benzenethiols, 2-sulfanylethanol, and 2-sulfanylacetic acid to N-[1-(dialkoxyphosphoryl)-2,2,2-trichloroethylidene]-arenesulfonamides was described in [12]. Furthermore, addition of alkanethiols [1,13], 2-sulfanylethanol [14], and 2-sulfanylacetic acid [15,16] to the activated C=N bond in N-(trichloroethylidene)arenesulfonamides was studied.…”

“…Furthermore, addition of alkanethiols [1, 13], 2-sulfanylethanol [14], and 2-sulfanylacetic acid [15,16] to the activated C=N bond in N-(trichloroethylidene)arenesulfonamides was studied. Polyfunctional S-adducts obtained in these reactions were then used to synthesize thiazolidine derivatives [12][13][14][15][16].Reactions of N-(trichloroethylidene)arenesulfonamides (that are readily obtained in one step from accessible N,N-dichloroarenesulfonamides and trichloroethylene [1]) with aromatic or heteroaromatic thiols were not reported previously. On the other hand, expected products of such reactions may be promising for the development of procedures for the preparation of fused heterocyclic systems, as well as of N-protected hetarylsulfanyl-substituted amino acids.…”

“…Such transformations provide convenient approaches to various functionalized sulfonamide derivatives [1][2][3][4][5][6][7][8][9][10][11][12][13][14] as interesting models for stereochemical studies [5-8] and reagents [1,[9][10][11][12][13][14][15][16].…”

“…Furthermore, addition of alkanethiols [1,13], 2-sulfanylethanol [14], and 2-sulfanylacetic acid [15,16] to the activated C=N bond in N-(trichloroethylidene)arenesulfonamides was studied. Polyfunctional S-adducts obtained in these reactions were then used to synthesize thiazolidine derivatives [12][13][14][15][16].…”