Characterization and Utility of N‐Unsubstituted Imines Synthesized from Alkyl Azides by Ruthenium Catalysis

Abstract

Shine a light: A fluorescent light‐induced synthetic method for the title compounds has been developed and the chemoselective nature of the reaction is highlighted by the observation of the cis/trans isomers of various N‐unsubstituted imines. The synthetic utility of this method is demonstrated by the one‐pot imine formation/asymmetric allylation sequence of benzyl azide catalyzed by 1. (Ipc=isopinocampheyl).

Novel Catalyst System for Hydrostannation of Alkynes

“…Recently we have reported the synthesis of I and its applications for the racemization of secondary alcohols in chemoenzymatic dynamic kinetic resolution, [9] the selective hydrosilylation of aldehydes, [10] and the generation of N-unsubstituted imines from alkyl azides. [11] The ruthenium complex I is a solid compound stable in air, but transforms into catalytic species simply by the illumination of household fluorescent light in solution state for the activation of CÀH [9] and SiÀH [10] bonds in the racemization of secondary alcohols and the selective hydrosilylation of aldehydes, respectively. The activation of azides involves the liberation of N 2 molecule and the 1,2-hydrogen shift from the a-carbon to the nitrogen.…”

“…The activation of azides involves the liberation of N 2 molecule and the 1,2-hydrogen shift from the a-carbon to the nitrogen. [11] It is well known that Ru radical species can be generated from the related diruthenium [CpRu(CO) 2 ] 2 complex under photolytic reactions. [12] Therefore, we envisioned that the combination of diruthenium complexes I-IV with trialkyltin hydrides might be useful in radical-mediated hydrostannation reaction.…”

Zinc‐Mediated syn‐Selective Crotylation of N‐Unsubstituted Imines

“…In light of this disappointing result, we reasoned that the unstable imine 2 might easily decompose under the reaction conditions. Addition of Et 3 B, based upon this analysis and related studies, improved the yield of the desired transformation (up to 80 %) and the diastereoselectivity (>11:1) when the reaction was performed at 0 °C. To ease the identification of the product, crude amine 3 was converted into the corresponding para ‐toluenesulfonyl amide in 75 % isolated yield (over three steps from the azide 1 ) with no loss of selectivity (entry 2).…”

Synthesis, QSAR and anticandidal evaluation of 1,2,3-triazoles derived from naturally bioactive scaffolds

“…The crude was extracted with ethyl acetate, washed with brine, dried over anhydrous sodium sulphate and concentrated under vacuum. The oily residue was used as such without any further purification [15].…”