An efficient, general procedure for highly chemoselective reductive mono-alkylation of ammonia with ketones is reported. Treatment of ketones with ammonia in ethanol and titanium(IV) isopropoxide, followed by in situ sodium borohydride reduction, and a straightforward workup afforded primary amines in good to excellent yields. Reductive alkylation of ammonia with aldehydes, on the other hand, a...

(Hetero)Aryl amines, an important class of organic molecules in medicinal chemistry, are most commonly synthesized from anilines, which are in turn synthesized by hydrogenation of nitroarenes. Amine synthesis directly from nitroarenes is attractive due to improved step economy and functional group compatibility. Despite these potential advantages, there is yet no general method for the synthesi...

A resin-capture and release strategy for making combinatorial 2,6,9-trisubstituted purine libraries is demonstrated by capturing N9-derivatized purines at the C6 position with a thio-modified polymer. The C2 fluoro group is subsequently substituted with primary and secondary amines followed by thioether oxidation and release by C6 substitution with amines and anilines. This approach complements...

The metal-free reduction of nitro compounds to amines mediated by trichlorosilane was successfully performed for the first time under continuous-flow conditions. Aromatic as well as aliphatic nitro derivatives were converted to the corresponding primary amines in high yields and very short reaction times with no need for purification. The methodology was also extended to the synthesis of two sy...

An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4'- t Bu2bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one N-oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic a...

The palladium-assisted one-pot three-component reactions of aldehydes, amines and olefins proceeded smoothly to give 2,6-unsubstituted 1,4-dihydropyridines (1,4-DHPs) using molecular oxygen as a sole oxidant. It also provides efficient Pd-catalyzed aerobic oxidation access to the anti-Markovnikov oxidative amination products of olefins from primary aromatic amines and alkenes. The method is ato...

We report a catalytic reductive alkylation reaction of primary or secondary amines with carboxylic acids. The two-phase process involves silane mediated direct amidation followed by catalytic reduction.

Preparation of 2-fluoroalkylbenzimidazoles from N-aryl trifluoroacetimidoyl (or bromodifluoroacetimidoyl) chlorides and primary amines has been achieved via copper(I)-catalyzed tandem reactions.

The asymmetric Michael addition of dioxindoles to β-substituted nitroalkenes is reported. The bifunctional primary amine-thiourea A, by means of a non-covalent-based mode of catalysis, secures direct access to 3-substituted 3-hydroxyoxindole derivatives with high stereocontrol.