Synthesis of Aziridines by Palladium‐Catalyzed Reactions of Allylamines with Aryl and Alkenyl Halides: Evidence of a syn‐Carboamination Pathway

Abstract

Crazy rings: Treatment of N‐arylallylamine with an aryl or alkenyl halide under palladium catalysis (see scheme; dba=dibenzylideneacetone, SPhos=2‐dicyclohexylphosphanyl‐2′,6′‐dimethoxybiphenyl) resulted in intramolecular cyclization to form the arylmethyl‐substituted aziridine with concomitant CC bond formation. The experiments for the elucidation of the reaction mechanism are also described.

Asymmetric Synthesis of α,α‐Disubstituted Allylic Amines through Palladium‐Catalyzed Allylic Substitution

“…The synthetic potential of these allylic amines was demonstrated by further transformation of 1 into the enantioenriched amide 36 , allylic nitrone 37 , asymmetric urea 38, and epoxide 39 through simple procedures (Figure ) with retention of the chiral integrity of the starting allylic amine. The α,α‐disubstituted allylic amines can also be transformed into highly functionalized aziridines as reported previously …”

Recent Developments in Palladium-Catalyzed Alkene Aminoarylation Reactions for the Synthesis of Nitrogen Heterocycles

“…28 A catalyst composed of Pd 2 (dba) 3 and S-Phos was effective for the coupling of allylic amines with aryl and alkenyl halides to yield a variety of substituted aziridines (Table 4). However, the presence of two large groups at C1 appears to be necessary, as substrates bearing small C1 groups (e.g.…”

Palladium-Catalyzed Heterofunctionalization of C-H, C=C and C≡ C Bonds

“…1), carboamination for the total synthesis of a cytotoxic alkaloid (±)-Tylophorine, 26 (eq. Synthesis of threemembered aziridine [78] and epoxide [79] rings can also be achieved, using S-Phos (27) and Ru-Phos (28), respectively (eq. 3) [77].…”