Arynes Promoted Dehydrosulfurization of Thioamides: Access to Nitriles and Diaryl Sulfides.

An aryne-promoted dehydrosulfurization reaction of thioamides to give nitriles and diaryl sulfides in a one-pot manner is presented. Aromatic, heteroaromatic, and aliphatic natural products and drug-derived nitriles and diaryl sulfides were obtained in good to excellent yields. Especially, selenoamide was also a suitable substrate and produced diaryl selenide and nitrile in high yields.

Synthesis of Sulfilimines via Multicomponent Reaction of Arynes, Sulfamides, and Thiosulfonates.

In this work, a facile and efficient method for the synthesis of sulfilimines through multicomponent reaction of arynes, sulfamides, and thiosulfonates was developed. A variety of structurally diverse substrates and functional groups were very compatible in the reaction, giving the corresponding sulfilimines in good to high yields. This protocol could be conducted on a gram scale, and the product was easily converted to sulfide and sulfoximine.

The organocatalytic synthesis of perfluorophenylsulfides the thiolation of trimethyl(perfluorophenyl)silanes and thiosulfonates.

The organic superbase -Bu-P-catalyzed direct thiolation of trimethyl(perfluorophenyl)silanes and thiosulfonates was developed. Yields of perfluorophenylsulfides of up to 97% under catalysis of 5 mol% -Bu-P were achieved. This method was shown to provide an efficient way to construct the perfluorophenyl-sulfur bond under mild metal-free reaction conditions.

An N-heterocyclic carbene-catalyzed switchable reaction of 9-(trimethylsilyl)fluorene and aldehydes: chemoselective synthesis of dibenzofulvenes and fluorenyl alcohols.

An N-heterocyclic carbene-catalyzed synthesis of dibenzofulvenes and fluorenyl alcohols was developed. In the presence of 10 mol% NHC (1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and 4 Å molecular sieves, 9-(trimethylsilyl)fluorene undergoes an olefination reaction with aldehydes to produce dibenzofulvenes in 43-99% yields. However, on reducing the NHC loading to 1 mol% and with the addition of water, 9-(trimethylsilyl)fluorene selectively undergoes nucleophilic addition with aldehydes to afford fluorenyl alcohols in 40-95% yields.

N-Heterocyclic carbene-catalyzed diastereoselective synthesis of sulfenylated indanes via sulfa-Michael-Michael (aldol) cascade reactions.

N-Heterocyclic carbene (NHC)-catalyzed diastereoselective synthesis of multisubstituted sulfenylated indanes has been developed. In the presence of 1 mol% NHC, various thiols underwent the sulfa-Michael-Michael cascade reaction with benzenedi(enones) efficiently to form the carbon-sulfur bond and construct sulfenylated indanes in good to excellent yields with high diastereoselectivity. In addition, the NHC-catalyzed sulfa-Michael-aldol cascade reaction between o-formyl chalcone and thiols has also been demonstrated to afford sulfenylated indanes with a free hydroxyl group in moderate yields and good diastereoselectivity.

Enhanced external counterpulsation inhibits intimal hyperplasia by modifying shear stress responsive gene expression in hypercholesterolemic pigs.

Background: Enhanced external counterpulsation (EECP) is a circulation assist device that may improve endothelial dysfunction by increasing shear stress. Chronic exposure of vascular endothelial cells and vascular smooth muscle cells to relatively high physiological shear stress has antiproliferative and vasoprotective effects. The present study hypothesizes that EECP inhibits intimal hyperplasia and atherogenesis by modifying shear stress-responsive gene expression.