Synthesis of Chiral Vicinal Diamines by Silver(I)‐Catalyzed Enantioselective Aminolysis of N‐Tosylaziridines

Abstract

The kinetic resolution of 2-aryl-N-tosylaziridines and the asymmetric desymmetrization of meso-N-tosylaziridines by ring openings with various primary and secondary anilines, and aliphatic amines as nucleophile have been realized by using a single silver(I)/chiral diphosphine complex as catalyst for the first time. The simple starting materials, broad scope, and easy scalability render this protocol a practical way to chiral vicinal diamine derivatives.

Catalytic Asymmetric Radical Diamination of Alkenes

“…Further studies including the expansion toward other substrate classes, product application, and the development of a more challenging intermolecular asymmetric version are ongoing in our laboratory. [1][2][3][4][5][6][7][8]…”

“…Chiral vicinal diamines represent key structural elements in a large number of natural products, pharmaceutical agents, and agrochemicals. [1][2][3][4][5][6][7][8] They also constitute excellent platforms for the development of chiral ligands, organocatalysts, and auxiliaries with broad utility in asymmetric synthesis. 9,10 Consequently, expedited assembly of vicinal diamines from readily available precursors has long been recognized as a preeminent goal in organic synthesis.…”

“…9,10 Consequently, expedited assembly of vicinal diamines from readily available precursors has long been recognized as a preeminent goal in organic synthesis. [1][2][3][4][5][6][7][8][11][12][13] In this regard, catalytic asymmetric diamination of unactivated alkenes with transition-metal or aryliodine(I) catalysts represents a straightforward and highly attractive method for creating such useful vicinal diamine scaffolds, given the facile accessibility of alkene starting materials. [14][15][16][17][18][19][20][21][22][23][24][25] However, the amine introduced by these asymmetric catalytic systems has to be masked by electron-withdrawing protecting groups, and direct incorporation of free alkylamine has so far remained elusive (Scheme 1A).…”

An Organocatalytic Kinetic Resolution of Aziridines by Thiol Nucleophiles

“…For example, catalytic asymmetric ring-opening of racemic aziridines by kinetic resolution has been demonstrated as an important strategy to provide expedient access to chiral amine derivatives with various vicinal functionalities (Scheme a). − This process also leads to enantioenriched aziridines that are themselves important precursors to other useful chiral building blocks via stereospecific transformations. Owing to these exceptional utilities, various catalytic systems, particularly based on metal catalysts, have been developed for this process in the past two decades. , While a range of nucleophiles, including carbon-, nitrogen-, and oxygen-based ones, have been demonstrated as versatile reaction partners, it is worth noting that the use of sulfur-based nucleophiles have remained challenging and scarce. Sometimes these nucleophiles may deactivate metal catalysts due to their strong coordination ability .…”

Synthesis of 2-Aminophosphates via SN2-Type Ring Openings of Aziridines with Organophosphoric Acids

“…As part of our continued interest in exploring the synthetic utility potential of aziridines, we describe herein a catalyst and metal-free way to 2-aminophosphates via direct ring opening of aziridines with organic phosphoric acids. The reaction features also a broad substrate scope, tolerating N -protected/unprotected aryl- and alkyl-substituted aziridines and could proceed in a highly enantiospecific way.…”