A highly efficient and environmentally-friendly base-mediated transition metal-free direct thiophilic catalytic approach is reported for the synthesis of -benzhydryl-phosphorothioates by reacting phosphite nucleophiles with diarylmethanethione. A wide variety of thioketones were coupled with different phosphite derivatives to provide the corresponding phosphorothioates in good to excellent yields. The control experiments and density functional theory (DFT) calculations rely on the regio-selective thiophilic addition of a phosphite nucleophile umpolung protocols.
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http://dx.doi.org/10.1039/d2cc04331a | DOI Listing |
Chem Commun (Camb)
September 2022
Department of Chemistry, National Chung Hsing University, Taichung City 402, Taiwan, (R.O.C.).
A highly efficient and environmentally-friendly base-mediated transition metal-free direct thiophilic catalytic approach is reported for the synthesis of -benzhydryl-phosphorothioates by reacting phosphite nucleophiles with diarylmethanethione. A wide variety of thioketones were coupled with different phosphite derivatives to provide the corresponding phosphorothioates in good to excellent yields. The control experiments and density functional theory (DFT) calculations rely on the regio-selective thiophilic addition of a phosphite nucleophile umpolung protocols.
View Article and Find Full Text PDFOrg Lett
September 2019
Center for Supramolecular Chemistry & Catalysis and Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, China.
We report a general activated amide to ester transformation catalyzed by CsCO. Using this approach, esterification proceeds under relatively mild conditions and without the need for a transition metal catalyst. This method exhibits broad substrate scope and represents a practical alternative to existing esterification strategies.
View Article and Find Full Text PDFInorg Chem
November 2018
State Key Laboratory of Elemento-Organic Chemistry and College of Chemistry , Nankai University, Tianjin 300071 , P. R. China.
Cesium carbonate-catalyzed oxidation of substituted phenylsilanes (ArSiH) in N, N-dimethylformamide (DMF) at room temperature for the efficient synthesis of polyhedral oligomeric silsesquioxanes (POSS) was described. This protocol allowed the rapid and selective access to several types of new POSS cages in modest to good yields under nonaqueous conditions. Depending on the bulkiness of the substituents on the phenyl rings, hexa- (T), octa- (T), and dodecaphenylsilsesquioxanes (T) can be selectively obtained.
View Article and Find Full Text PDFOrg Lett
April 2018
State Key Laboratory of Natural Medicines, Department of Organic Chemistry , China Pharmaceutical University, Nanjing , 210009 , P. R. China.
In this work, we present a strategy for the stereoselective synthesis of functionalized benzooxazepino[5,4- a]isoindolone derivatives via a CsCO-catalyzed domino β-addition and γ-aldol reaction of 2-(2-hydroxyphenyl)isoindoline-1,3-dione derivatives with allenoates, which offers an avenue for a combination of the structural unity between benzooxazepine and isoindolone motifs in synthetically useful yields with high stereoselectivities under mild conditions. Remarkably, it is the first example of highly stereoselective CsCO-catalyzed formal [5 + 2] annulation of 2-(2-hydroxyphenyl)isoindoline-1,3-dione with allenoates.
View Article and Find Full Text PDFChemistry
July 2014
State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071 (P. R. China), Fax: (+86) 22-23503461.
Cs2CO3 has been found to be an efficient and chemoselective catalyst for reduction of aldehydes and ketones to alcohols with one equivalent of Ph2SiH2 as the reductant under solvent-free conditions. Most of the aldehydes employed can be effectively hydrosilated quantitatively to give the corresponding silyl ethers in 2 h at room temperature, whereas the hydrosilylation of ketones proceeded smoothly at 80 °C. The catalyst system tolerates a number of functional groups including halogen, alkoxyl, olefin, ester, nitro, cyano, and heteroaromatic groups; the selective hydrosilylation of aldehydes in the presence of ketone can be effectively controlled by temperature; and hydrosilylation of α,β-unsaturated carbonyls resulted in the 1,2-addition products.
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