Palladium‐Catalyzed Thiocarbonylation of Benzyl Chlorides with Sulfonyl Chlorides for the Synthesis of Arylacetyl Thioesters

Abstract

A convenient procedure for the synthesis of thioesters has been developed via a palladiumcatalyzed thiocarbonylation of benzyl chlorides with sulfonyl chlorides. Various arylacetyl thioesters were produced in good yields by using sulfonyl chlorides as an odorless sulfur source. Furthermore, W(CO) 6 exhibited dual roles as both a solid CO surrogate and reductant here.

Synthetic Strategies for Versatile Thioester Building Blocks

“…Unlike the alkene substrates, the hydrothiocarbonylation of alkyne was less extensively studied by various groups over 25 years. [9] Recently, in 2019, the Shang group described the decarboxylative hydrothiocarbonylation of alkynes (35) with oxalic acid monothioester (17) towards thioesters (36) under Pd-catalysis, albeit very narrow scopes of alkyne and thiol (Scheme 5a). [15] Afterwards, in 2021, Wu and co-workers demonstrated a ligand-controlled regiodivergent hydrothio-carbonylation of aromatic and aliphatic alkynes (26) with CO gas and free thiols (27) to furnish thioester derivatives (28&29) in high linear as well as branched selectivity (Scheme 10).…”

“…In 2021, the Qi and Wu group disclosed a synthetic method, en route to arylacetyl thioesters ( 80 ) featuring electron‐rich and electron‐deficient functionalities, from various benzyl chlorides ( 78 ), arylsulfonyl chlorides ( 79 ) as thiol precursors and W(CO) 6 as the surrogate of CO as well as reductant under palladium catalysis regime (Scheme 21). [36] Notably, the yield of thioester was drastically influenced by the concentration of the reaction mixture, such as the product selectivity was considerably enhanced by decreasing the concentration. As proposed by the authors, the oxidative addition of benzyl chloride to Pd(0) leads to the formation of benzyl palladium species that is converted to acyl palladium complex with CO from W(CO) 6 .…”

Palladium-Catalyzed Denitrogenative Carbonylation of Benzotriazoles with Cr(CO)6 as the Carbonyl Source

“…In 2002, Mo­(CO) 6 was first applied to the palladium-catalyzed aminocarbonylation of aryl bromides and iodides under microwave conditions by the group of Larhed and co-workers . Subsequently, much of the literature on carbonylation is extensive and focuses on using different metal–carbonyl complexes including Cr­(CO) 6 , W­(CO) 6 , Co 2 (CO) 8 , etc. as bench-stable solid C1 sources.…”

Chemo-Biocascade Reactions Enabled by Metal–Organic Framework Micro-Nanoreactor

“…However, the reaction conditions of biocatalysts are usually different from those of the chemocatalysts in that the two types of catalysts are frequently deactivated in the one-pot reaction process [ 6 ]. Generally speaking, some biocatalysts (enzymes) prefer the aqueous phase reaction system at relatively low temperature [ 9 , 10 ], whereas the chemocatalysts favor the organic phase at high temperature [ 11 ]. Also, the matching between chemical catalysts' and biocatalysts' activity is also a challenging issue [ 12 , 13 ].…”