Catalytic Asymmetric Construction of β-Azido Amides and Esters via Haloazidation

Abstract

A catalytic regio- and enantioselective haloazidation reaction with a chiral iron­(II) complex catalyst under mild reaction conditions was reported. By this approach, the stereoselective α-halo-β-azido difunctionalization of both α,β-unsaturated amides and α,β-unsaturated esters was achieved. This method enabled the construction of a broad spectrum of valuable functionalized amides and esters, including enantiomerically enriched β-azido amides, aziridine amides, α-amino amide derivatives, β-triazole amides, functionalized peptide derivatives, and α-halo-β-azido-substituted esters.

Feng Ligand: Privileged Chiral Ligand in Asymmetric Catalysis

“…By exploiting the same strategy, they further reported intramolecular asymmetric haloaminocyclization reactions, [ 40e ] asymmetric bromoamination reactions with NBS as both bromine and amide source, [ 40f ] asymmetric Intra‐ and Intermolecular haloetherification reactions, [ 41 ] asymmetric halohydroxylation reactions [ 42 ] as well as haloazidation reactions, [ 43 ] reflecting the general applicability of the N , N '‐dioxide‐metal complex.…”

Recent Progress in the Asymmetric Syntheses of α‐Heterofunctionalized (Masked) α‐ and β‐Amino Acid Derivatives

“…[26] More, recently, Liu, Feng, and co-workers developed a chiral Fe-catalyzed protocol for the aza-Michael addition of TMSN 3 with direct bromination of the α-position, giving the versatile products 46 with excellent diastereo-and enantioselectivities (Scheme 10B). [27] Scheme 10. Asymmetric aza-Michael-initiated syntheses of α-halogenated--AA.…”

Chiral <italic>N</italic>,<italic>N</italic>ʹ-dioxide and their metal complexes in asymmetric catalysis

“…[44] 和卤叠氮化反应 [45,46] . 以 (Cl、Br、I)叠氮化反应 [45,46] , 该反应具有良好的底物普 配合物高效催化硝基烷烃对α,β-不饱和吡唑酰胺的Mi-chael加成反应 [53] , 高效高选择性合成了手性抗癫痫药 物普瑞巴林和治疗肌肉痉挛药物巴氯芬.…”