Synthesis of Thiazolidine‐2‐thiones through a One‐Pot A³‐Coupling–Carbon Disulfide Incorporation Process

Abstract

A copper‐catalyzed two‐step one‐pot procedure for the synthesis of thiazolidine‐2‐thiones has been developed. The process involves a three‐component coupling of an alkyne, an aldehyde, and an amine (A3‐coupling) followed by trapping the resulting propargylamine with carbon disulfide and subsequent cyclization.

Activation of Primary Amines by Copper(I)-Based Lewis Acid Promoters in the Solventless Synthesis of Secondary Propargylamines

“…Many synthetic methods have been developed for the synthesis of different classes of heterocycles [1][2][3][4][5][6][7][8][9][10] starting from propargylamines. At the same time, propargylamines are direct precursors of propargylureas that can undergo silver-or gold-catalyzed cycloisomerization to produce a series of other nitrogen-containing heterocyclic compounds.…”

Synthesis of Chiral Propargylamines, Chiral 1,2‐Dihydronaphtho[2,1‐b]furans and Naphtho[2,1‐b]furans with C‐Alkynyl N,N′‐di‐(tert‐butoxycarbonyl)‐aminals and β‐Naphthols

“…Three anhydrous additives, MgSO 4 , Na 2 SO 4 and 3 Å MS, were attempted (entries 10-12), and Na 2 SO 4 provided 90 % ee value (entry 11). We investigated the affection of reaction temperature and time (compare entries 9, [13][14][15][16][17], and found that 60°C and 12 h were suitable (entry 16). Other solvents were attempted, and the results showed that toluene was optimal (see Table S1).…”

“…[5] The reactions with propargylamines as the substrates can provide miscellaneous heterocyclic compounds [6] such as pyrroles, [7] pyrrolines, [8] pyrrolidine, [9] pyrazines, [10] pyrazoles, [11] pyridines, [12] dihydropyridines, [13] isoxazoles, [14] oxazolidines, [15] thiazoles [16] and thiazolidines. [17] The common methods for synthesis of chiral propargylamines include the asymmetric alkynylation of imines [18,19] and the catalytic asymmetric addition of nucleophiles to previously prepared [20] or in situ generated [21,22] Calkynyl imines (Scheme 1a). In 2016, Shao and co-workers reported the catalytic asymmetric arylations of C-alkynyl imines leading to chiral propargylamines with C-alkynyl N-Boc-protected N,O-acetals and phenols as the substrates.…”

A3 Coupling Reaction in the Synthesis of Heterocyclic Compounds

“…Van der Eycken and co‐workers developed a Cu(I)‐catalyzed one‐pot two‐step procedure for the synthesis of thiazolidine‐2‐thiones from primary amines 1 p , aldehydes 2 , alkynes 3 , and carbon disulfide (Scheme 34). [79] The in situ generated propargylamines 4 were shown to react with CS 2 in the presence of 15 mol% CuBr in toluene at 100 °C to form thiazolidine‐2‐thiones 127 . A plausible mechanism for this transformation includes formation of carbamodithioic acid intermediate 128 undergoing 5‐exo‐dig cyclization via attack of the sulfur center at the triple bond.…”