Gold(I)-Catalyzed Highly Regio- and Stereoselective Decarboxylative Amination of Allylic N-Tosylcarbamates via Base-Induced Aza-Claisen Rearrangement in Water

Abstract

A gold(I)-catalyzed decarboxylative amination of allylic N-tosylcarbamates via base-induced aza-Claisen rearrangement has been developed. A variety of substituted N-tosyl allylic amines were obtained in good yield, excellent regioselectivity, and high to excellent stereoselectivity. This transformation could be performed either in H(2)O or in one pot directly from allylic alcohols and therefore represents an efficient and environmentally benign protocol for the synthesis of N-tosyl allylic amines.

Enantioselective Chemo‐ and Biocatalysis: Partners in Retrosynthesis

“…[156] 3.3. [157] Thec omparable chemocatalytic process to access the same products would involve Ircatalyzed allylic substitution, which has been demonstrated enantioselectively by the groups of Hartwig, [158] Yang, [159] You, [160] Helmchen [161] and Carreira. [157] Thec omparable chemocatalytic process to access the same products would involve Ircatalyzed allylic substitution, which has been demonstrated enantioselectively by the groups of Hartwig, [158] Yang, [159] You, [160] Helmchen [161] and Carreira.…”

Gold versus silver-catalyzed amination of allylic alcohols

“…The following compounds (E)-N-(1,3-diphenylallyl)-4-methylbenzenesulfonamide (3aa) [7], (E)-N-(1,3-diphenylallyl)-4-methylbenzenesulfonamide (3ab) [7], (E)-4-chloro-N- (1,3-diphenylallyl) benzenamine (3ag) [8a], (E)-N-(1,3-diphenylallyl)-4-nitroaniline (3ah) [2], (E)-N-(1,3-diphenylallyl)-4-methylaniline (3ai) [8a], (E)-N-(but-2-enyl)-4-methylbenzenesulfonamide (3ba) [13], (E)-4-methyl-N-(penta-2.4-dienyl)benzenesulfonamide (3ca) [13], N-(cyclohex-2-enyl)-4-methylbenzenesulfonamide (3da) [7], and (E)-4-methyl-N-(4-phenylbut-3-en-2-yl)benzenesulfonamide (3ea) [7] have been previously described. Physical and spectroscopic data of the other synthesized compounds follow.…”

Highly efficient gold(I)-catalyzed Overman rearrangement in water

“…With this substrate, the catalytic activities of different gold(I) complexes in H 2 O were examined. When 1a was subjected to the optimal catalytic conditions previously reported by our group (5 mol % AuCl/AgOTf at 75 °C) [29], the desired allylic trichloroacetamide 2a was obtained in 91% yield in a reaction time of 1 h (Table 1, entry 1). Gold(I) complexes with phosphine ligands, Au(PPh 3 )Cl or Au[P( t -Bu) 2 ( o -Ph)Ph]Cl, in place of AuCl gave none of the desired product (Table 1, entries 2 and 3).…”

“…However, when they were used as catalysts for the Overman rearrangement, the substrate scope was limited and only poor to moderate yields were achieved [25–28]. Very recently, our group developed an efficient gold(I)-catalyzed decarboxylative aza-Claisen rearrangement of allylic N -tosylcarbamates for the synthesis of N -tosyl allylic amines [29]. This reaction was performed in water and therefore represented an environmentally benign protocol [30–34].…”