An operationally simple and efficient one-pot protocol for the synthesis of highly functionalized thiazolidin-4ones and thiazolines has been devised via Rh(OAc) 2 -catalyzed annulative coupling of β-ketothioamides with diazo compounds under mild reaction conditions for the first time. This double functionalization of diazo compounds proceeds via selective Salkylation followed by intramolecular N-cyclization enabling the formation of C−S and C−N bonds at moderate temperature. Notably, the products possess Z-stereochemistry with regard to the exocyclic CC double bond at the 2-position of the ring. Further, the synthetic utility of the strategy has been revealed to access 2,3-dihydrobenzo[d]thiazoles. Remarkably, atom economy and tolerance of a wide range of functional groups are added characteristics to this strategy.
A photocatalyst‐ and additive‐free, visible‐light‐mediated chemoselective domino protocol was devised to access fully substituted thiazoline derivatives from β‐ketothioamides and α‐diazo 1,3‐diketones at moderate temperature in open air. The reaction proceeds through in situ generation of electrophilic carbenes from α‐diazo 1,3‐diketones by a low‐energy blue LED (448 nm), which undergoes selective coupling with nucleophilic β‐ketothioamides to give thiazolines by successive formation of C−S and C−N bonds in one stretch. Notably, the benign and clean conditions, operational simplicity, sustainability, 100 % carbon economy, high yields, and wide functional‐group tolerance are further attributes of the strategy. A mechanistic rationale for this cascade reaction sequence is well supported by control experiments.
An efficient protocol for visible-light-mediated
synthesis of a
specific class of 1,2,4-dithiazolidines from β-ketothioamides
is devised employing eosin Y as a photoinitiator at ambient temperature
in an open pot. The reaction proceeds via an in situ-generated thiyl
radical followed by dimerization/deaminative cyclization cascade,
enabling the creation of a dithiazolidine ring through successive
formation of S–S and N–C bonds under metal- and additive-free
conditions. Remarkably, the benign conditions, sustainability, and
quantifying forbearance of wide horizons of functional groups are
added characteristics to the strategy. The developed hydrogen-atom-transfer
methodology will be helpful in postsynthetic modification via added
synthetic handles.
An efficient chemoselective practical route to fully substituted thiazoles and 2,3-dihydrothiazoles has been devised by [4 + 1] heterocyclization of α-(N-hydroxy/aryl)imino-β-oxodithioesters with in situ generated Cu-carbenoids of diazocarbonyls. The α-(N-hydroxy/aryl)imino-β-oxodithioesters are readily accessible by the reaction of β-oxodithioesters with nitrous acid/nitrosoarenes. The overall transformation involves sequential N-O/C-N bonds cleavage followed by cascade C-N/C-S bonds formation in one-pot. This new strategy allows full control over the introduction of various sensitive functional groups at different positions of the thiazole ring, broadening the arsenal of synthetic methods to obtain such scaffolds.
Phosphonium ylides are being reported here as a catalyst for the formation of thiazolidines and 1,3-thiazinanes from β-ketothioamides with dihaloalkanes via [3 + 2] and [3 + 3] annulations under metal-free conditions.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.