New chiral diamide ligands: synthesis and application in allylic alkylation

A new family of chiral diamide ligands has been designed and synthesised. These ligands have been successfully applied to an asymmetric allylic substitution reaction. A palladium complex of one of the diamide ligands achieved enantioselectivities of up to 93% in the allylic alkylation of 1,3-diphenyl-3-acetoxyprop-1-ene.

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UNIFIDE (2S)-5-Oxo-N-(pyridin-2-ylmethyl)pyrrolidine-2-carboxamideC11H13N3O2[α]D20=-22.2 (c 0.5, chloroform)Source of chirality: (S)-(−)-2-pyrrolidone-5-carboxylic acidAbsolute configuration: (2S)

CROSIDE N-{[(2S)-5-Oxopyrrolidin-2-yl]methyl}pyridine-2-carboxamideC11H13N3O2[α]D20=+41.1 (c 5.0, ethanol)Source of chirality: (S)-(−)-2-pyrrolidone-5-carboxylic acidAbsolute configuration: (2S)

(S)-5-Oxopyrrolidine-2-carboxylic acid ethyl esterC7H11NO3[α]D20=+2.4 (c 10, ethanol)Source of chirality: (S)-(−)-2-pyrrolidone-5-carboxylic acidAbsolute configuration: (S)

Methyl-(S)-2-pyrrolidinone-5-carboxylateC6H9NO3[α]D20=-8.2 (c 1.0, dichloromethane)Source of chirality: (S)-(−)-2-pyrrolidone-5-carboxylic acidAbsolute configuration: (S)

(S)-5-(Hydroxymethyl)-2-pyrrolidoneC5H9NO2[α]D20=+28.0 (c 5.0, ethanol)Source of chirality: (S)-(−)-2-pyrrolidone-5-carboxylic acidAbsolute configuration: (S)

(2S)-5-Oxopyrrolidin-2-yl methyl methanesulfonateC6H11NO4S[α]D20=+16.2 (c 1.02, ethanol)Source of chirality: (S)-(−)-2-pyrrolidone-5-carboxylic acidAbsolute configuration: (2S)

(S)-5-(Azidomethyl)-2-pyrrolidoneC5H8N4O[α]D20=+72.8 (c 5.0, ethanol)Source of chirality: (S)-(−)-2-pyrrolidone-5-carboxylic acidAbsolute configuration: (S)

(S)-5-(Aminomethyl)-2-pyrrolidoneC5H10N2O[α]D20=+33.4 (c 5.0, ethanol)Source of chirality: (S)-(−)-2-pyrrolidone-5-carboxylic acidAbsolute configuration: (S)