2,6-Di(hetero)aryl and 2-(hetero)aryl substituted dithienothiazines are prepared from N-aryl dithienothiazines by a lithiation–lithium–zinc exchange–Negishi cross-coupling sequence with (hetero)aryl iodides in a one-pot fashion in good to excellent yields. These novel extended π-electron systems can be reversibly oxidized and fine-tuned in their electronic properties as supported by cyclo volta...

Palladium-catalyzed cross-coupling of aryl bromides with 2-aryl-1,3-dithianes is described. This methodology takes advantage of the relatively acidic benzylic proton of the dithiane, allowing it to act as a competent, polarity-reversed transmetalation reagent. This unique approach affords the ability to employ an orthogonal deprotection strategy, and practical routes to both diaryl ketones and ...

A novel family of chiral ortho-substituted BINAPO ligands (o-BINAPO) were synthesized from BINOL, and their Ru complexes were highly efficient catalysts for asymmetric hydrogenation of beta-aryl-substituted beta-(acylamino)acrylates and beta-aryl-substituted beta-keto esters. The Ru-bisphosphinite catalysts can tolerate an E/Z mixture of beta-aryl-substituted beta-(acylamino)acrylates. These hi...

Phenols and aryl thiols are fundamental building blocks in organic synthesis and final products with interesting biological activities. Over the past decades, substantial progress has been made in transition-metal-catalyzed coupling reactions, which resulted in the emergence of new methods for the synthesis of phenols and aryl thiols. Aryl halides have been extensively studied as substrates for...

Iodine-methanol mediated oxidative-aromatization of 2-aryl-6,8-dibromo-2,3-dihydroquinolin-4(1H)-ones afforded the corresponding 2-aryl-6,8-dibromo-4-methoxy-quinolines in high yield and purity. The isomeric 1-(2-amino-3,5-dibromophenyl)-3-aryl-2-propen-1-ones reacted with iodine in methanol afford in a single pot operation the corresponding 2-aryl-6,8-dibromo-4-methoxyquinoline (major) and 2-...

We report the arylation and heteroarylation of α,α-difluoro-α-(trimethylsilyl)acetamides with aryl and heteroaryl bromides catalyzed by an air- and moisture-stable palladacyclic complex containing P(t-Bu)2Cy as ligand. A broad range of electronically varied aryl and heteroaryl bromides underwent this transformation to afford α-aryl-α,α-difluoroacetamides in high yields. Due to the electrophilic...

We report the palladium-catalyzed coupling of aryl halides with ammonia and gaseous amines as their ammonium salts. The coupling of aryl chlorides and ortho-substituted aryl bromides with ammonium sulfate forms anilines with higher selectivity for the primary arylamine over the diarylamine than couplings with ammonia in dioxane. The resting state for the reactions of aryl chlorides is different...

We report the first atomistic level description of the handedness inversion mechanism for helical arylamide foldamers. The key process in the handedness inversion is the simultaneous unfolding and folding of two adjacent aryl-aryl linkages, propagating from a helix terminus along the strand. Intermediates along the inversion pathway have a common feature - a single unfolded aryl-aryl linkage (t...

An efficient and straightforward method for one-pot synthesis of aryl azides from the corresponding amines, employing tributylstannyl azide as transfer reagent of N3 group is described. In this procedure diazotization of aryl amines occurs under mild conditions using tert-butyl nitrite (t-BuONO) and p-toluenesulfonic acid (TsOH). A variety of substituted aryl amines, with both electron-withdraw...

Aminocarbonylation of aryl halides is one of the most useful methods in amide synthesis, but nitroarenes have not been used as a nitrogen source in this method even though they are more economical and accessible than anilines. Reported here is the development of nickel catalysis for the first three-component reactions of aryl halides, Co2(CO)8, and nitroarenes under reductive conditions to prod...