Methods for the direct synthesis of thioesters from aldehydes: a focus review (original) (raw)
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Continuous flow as a benign strategy for the synthesis of Thioesters via selective C-N bond cleavage
Journal of Flow Chemistry, 2020
A metal-free C-N bond cleavage of amide functionality has been reported for the efficient and rapid synthesis of thioester in a simple flow system. The feasibility of this method has been investigated with various aliphatic and aromatic thiols with Nacylamide derivatives to deliver the corresponding thioesters. The fruitful outcome of this process includes good to excellent yields, broad functional group compatibility and can afford the thioesters in just 40 s.
Org. Chem. Front. 2018, 5(16), 2447-2452., 2018
Thioesters were synthesized via palladium-catalyzed carbonylation of thioacetates and aryl iodides. S-Aryl thioacetates coupled with carbon monoxide and aryl iodides to afford the desired S-aryl thioesters in good yields. The reaction showed good functional group tolerance toward fluoro, chloro, ketone, ester, aldehyde, cyano, and nitro groups. The tandem reaction of the direct S-arylation of aryl iodides from potassium thioacetate (KSAc) and subsequent carbonylation of the intermediates S-aryl thioacetates provided S-aryl thioesters in moderate-to-good yields.
Palladium-Catalyzed Decarbonylative Thioetherification of 2-Pyridyl Thioesters
Wang, S.-F. Li, C-E.: Liu, Y.-C.; Reddy, D. M.; Basha, R. S.; Park, J. K.; Lee, S.; Lee, C.-F. Asian J. Org. Chem. 2020, 9(11), 1826-1833, 2020
An efficient palladium-catalyzed intramolecular decarbonylative thioetherification of 2-pyridyl thioesters to furnish 2-pyridyl aryl or alkyl thioethers is reported. Notably, PdCl 2 /PPh 3 is found to be an effective catalytic system for decarbonylative thioetherification of 2-pyridyl thioesters and is compatible under elevated temperature and strong basic conditions. This unique strategy is simple in operation and practice, uses a cheap metal-ligand catalytic system, affords the products in high yields, and has high functional group tolerance. In addition, other heterocyclic thioesters such as fur-2-yl, thiophene-2-yl, quinolin-2-yl and isoquinolin-1-yl thioesters are also consistent under the optimized reaction conditions.
Peptide Thioester Synthesis via an Auxiliary-Mediated N–S Acyl Shift Reaction in Solution
International Journal of Peptide Research and Therapeutics, 2007
The 4,5-dimethoxy-2-mercaptobenzyl (Dmmb) group attached to a main chain amide in a peptide is easily transformed into an S-peptide via an intramolecular N-S acyl shift reaction under acidic conditions, and the S-peptide produces a peptide thioester through an intermolecular thiol-thioester exchange reaction. In order to develop a method for efficiently preparing peptide thioesters based on the N-S acyl shift reaction, the factors involved in this process were analyzed in detail. The general features of the transformation at the Dmmb group attached amide bond in a trifluoroacetic acid (TFA) solution and the generation of a peptide thioester were examined by 13 C-NMR spectral measurements, reversed-phase (RP) HPLC analyses, mass measurements, and amino acid analyses. The methoxy group of the Dmmb group was not essential for the N-S acyl shift reaction, but played a role in stabilizing the thioester form. The addition of water to the TFA solution accelerated the N-S acyl shift reaction mediated by the Dmmb group and also suppressed the acid-catalyzed cleavage of the Dmmb group. A peptide thioester was produced from the S-peptide via an intermolecular thiol-thioester exchange reaction with minimal epimerization of the amino acid residue that constituted the thioester bond. Undesirable side reactions, such as the hydrolysis of the thioester bond and an S-N acyl shift reaction occurred during the synthetic process, which is a subject of further investigation.