S-Alkylation of dithiocarbamates via a hydrogen borrowing reaction strategy using alcohols as alkylating agents

Abstract

Herein, we report an operationally simple, environmentally benign and scalable approach towards the synthesis of S-benzyl/alkyl dithiocarbamates via hydrogen borrowing reaction between alcohol and dithiocarbamate anion, catalyzed by the hydroxyapatite-supported...

Direct C−H Sulfuration: Synthesis of Disulfides, Dithiocarbamates, Xanthates, Thiocarbamates and Thiocarbonates

“…As for the preparation of dithiocarbamates (Scheme 2), typical methods include: a) nucleophilic substitutions of thiophosgene, thiocarbamoyl chlorides or chlorodithioformates by thiols and/or amines; [28] b) additions of thiols to potassium thiocyanate [29] or isothiocyanates; [30] c) two-component reactions of tetraalkylthiuram disulfides with compounds such as alkenes, [31] diaryliodonium salts, [32] aryl halides, [33] arylboronic acids, [34] arylsilanes, [35] organometallic reagents, [36] diaryl disulfides [37] and anilines; [38] d) two-component reactions of dithiocarbamate salts with compounds such as aryl iodides, vinyl bromides, [39] arylboronic acids, [40] diaryliodonium salts [41] and alcohols; [42] e) three-component reactions between amines, carbon disulfide and alkyl donors such as alkenes, [43] alkyl halides, [44] alcohols, [45] epoxides, [46] cyclopropanes, [47] αdiazoesters, [48] sulfoxonium ylides, [49] sulfonium or sulfoxonium iodides, [50] or aryl donors such as aryl iodides/bromides, [51] pentafluorobenzonitrile, [52] arylboronic acids, [53] diaryliodonium salts, [54] aryldiazonium salts [55] and 2-(trimethylsilyl)aryl triflates; [56] f) electron donor-acceptor (EDA) photoactivationpromoted syntheses from CS 2 , amines and compounds such as Katritzky salts, [57] aryl halides, [58] dibenzothiophenium salts [14q] and aryl thianthrenium salts; [59] g) three-component reactions between isocyanides, thiols and sulfur [60] or H 2 S; [61] h) fourcomponent reactions between thiosulfate salts, K 2 S, CHCl 3 and amines. [62] Rega...…”

Multicomponent synthesis via acceptorless alcohol dehydrogenation: an easy access to tri-substituted pyridines

“…Recently, our group reported on a hydroxyapatite-supported copper nano-catalyst for direct C(sp 3 )-S coupling between alcohols and dithiocarbamate anions via the borrowing hydrogen strategy. 27 a With our continued interest in exploring the novel applications of acceptorless dehydrogenation reactions, 27 we report here palladium supported on a hydroxyapatite catalyst for the synthesis of tri-substituted pyridines using ammonium acetate as the nitrogen source via an acceptorless alcohol dehydrogenation strategy.…”