- Rh(I)-Catalyzed Intramolecular Decarbonylation of Thioesters
-
Decarbonylative synthesis of thioethers from thioesters proceeds in the presence of a catalytic amount of [Rh(cod)Cl]2 (2 mol %). The protocol represents the first Rh-catalyzed decarbonylative thioetherification of thioesters to yield valuable thioethers. Notable features include the absence of phosphine ligands, inorganic bases, and other additives and excellent group tolerance to aryl chlorides and bromides that are problematic using other metals to promote decarbonylation. Gram scale synthesis, late-stage pharmaceutical derivatization, and orthogonal site-selective cross-couplings by C-S/C-Br cleavage are reported.
- Cao, Han,Liu, Xuejing,Bie, Fusheng,Shi, Yijun,Han, Ying,Yan, Peng,Szostak, Michal,Liu, Chengwei
-
p. 10829 - 10837
(2021/07/28)
-
- Halide-Accelerated Acyl Fluoride Formation Using Sulfuryl Fluoride
-
Herein, we report a new one-pot sequential method for SO2F2-mediated nucleophilic acyl substitution reactions starting from carboxylic acids. A mechanistic study revealed that SO2F2-mediated acid activation proceeds via the anhydride, which is then converted to the corresponding acyl fluoride. Tetrabutylammonium chloride or bromide accelerate the formation of acyl fluoride. Optimized halide-accelerated conditions were used to synthesize acyl fluorides in 30-80percent yields, and esters, amides, and thioesters in 72-96percent yields without reoptimization for each nucleophile.
- Foth, Paul J.,Malig, Thomas C.,Yu, Hao,Bolduc, Trevor G.,Hein, Jason E.,Sammis, Glenn M.
-
supporting information
p. 6682 - 6686
(2020/09/02)
-
- Thioesterification and Selenoesterification of Amides via Selective N-C Cleavage at Room Temperature: N-C(O) to S/Se-C(O) Interconversion
-
The direct nucleophilic addition to amides represents an attractive methodology in organic synthesis that tackles amidic resonance by ground-state destabilization. This approach has been recently accomplished with carbon, nitrogen and oxygen nucleophiles.
- Li, Guangchen,Rahman, Md. Mahbubur,Szostak, Michal
-
supporting information
p. 1060 - 1066
(2020/04/01)
-
- One-pot odourless synthesis of thioesters via in situ generation of thiobenzoic acids using benzoic anhydrides and thiourea
-
An efficient and odourless procedure for a one-pot synthesis of thioesters by the reaction of benzoic anhydrides, thiourea and various organic halides (primary, allylic, and benzylic) or structurally diverse, electron-deficient alkenes (ketones, esters, and nitriles) in the presence of Et3 N has been developed. In this method, thiobenzoic acids were in situ generated from the reaction of thiourea with benzoic anhydrides, which were subjected to conjugate addition with electron-deficient alkenes or a nucleophilic displacement reaction with alkyl halides.
- Abbasi, Mohammad,Khalifeh, Reza
-
p. 1265 - 1273
(2015/08/18)
-
- Iron-catalyzed synthesis of thioesters from thiols and aldehydes in water
-
The preparation of thioesters through the iron-catalyzed coupling reaction of thiols with aldehydes is described. The reactions were carried out by using tert-butyl hydroperoxide (TBHP) as an oxidant and water as a solvent in most cases. This system is co
- Huang, Yu-Ting,Lu, Shao-Yi,Yi, Chih-Lun,Lee, Chin-Fa
-
p. 4561 - 4568
(2014/06/09)
-
- Reductive cleavage of C - S bond by samarium diiodide: A novel method for the synthesis of disulfides and thiolesters
-
Disulfides were obtained by the reaction of thiocyanates with equivalent SmI2. Smarium thiolates were generated by the reaction of an equivalent of thiocyanates with two equivalents of SmI2, and then reacted smoothly with acyl chlorides to give thiolesters.
- Jia, Xueshun,Zhang, Yongmin,Zhou, Zunjun
-
p. 8833 - 8834
(2007/10/02)
-