Highly Selective Preparation of a Chiral Quaternary Allyl Aryl Piperidinedione by Palladium‐Catalyzed Asymmetric Allylation Under Solid–Liquid Phase‐Transfer Catalysis

Abstract

The combination of a chiral palladium catalyst and a solidliquid phase-transfer catalyst provides an effective method for the chemo-and enantioselective preparation of the chiral quaternary center of an allyl aryl piperidinedione.

Enantioselective Copper-Catalyzed Intermolecular Cyanobenzoyldifluoromethylation of Alkenes: Access to Chiral β-Difluoroacyl Nitriles

“…The product 4b could be used to prepare tetrafluoroalkylated nitrile 7a without loss of enantiopurity (90% ee). The carboxylic acid 7b could be easily acquired with good enantioselectivity (85% ee). The product 4b was treated with NaBH 4 to afford the desired product β-difluoro-γ-hydroxy nitrile 7c but with 4% enantiomeric excess (see the SI for details).…”

Copper‐Catalyzed Enantioselective Cyano(Fluoro)Alkylation of Alkenes

“…The cyanofluoroalkylation product 5 a can react with ethanolamine to afford product fluoroalkylated oxazole ( 9 ) in 82% yield but with no enantiomeric excess. Similarly, the γ‐cyanoester ( 6 i ) can be cyclized to form a racemic phenyl‐substituted piperidine‐2,6‐dione ( 10 ) in 62% yield …”

Transition Metal-Catalyzed α-Position Carbon–Carbon Bond Formations of Carbonyl Derivatives

“…Although a plethora of transition metal-catalyzed asymmetric allylic alkylations have been reported (see the allylation references in Table 1), controlling the stereoselectivity of the generated quaternary center is challenging, and the substrate scope is largely limited to the amide moiety. In 2007, a chiral aryl allyl glutarimide was synthesized by the direct alkylation of glutarimide enolates (Scheme 34) [46]. The chemo-, regio-, and stereoselective reaction employed a catalytic amount of nHex 4 NBr and a highly reactive C-nucleophile to deliver the chiral quaternary carbon center with no N-allylation being observed.…”

“…Pd catalyst and monodentate phosphine ligand Aldehydes Allylation [14] Arylation [15][16][17] Imines Allylation [41][42][43] Pd catalyst and DPPF ligand Ketones Allylation [33,34] Pd catalyst and diphenylbisphosphine ligand Ketones Allylation [31] Amides Allylation [46,47] Pd catalyst and dialkylbisphosphine ligand Amides Arylation [48] Pd catalyst and pyrrolidine organocatalyst Aldehydes Allylation [18,19] Pd catalyst and phosphoric acid Aldehydes Allylation [20][21][22][23] Pd catalyst and DIAPHOX ligand Ketones Allylation [32] Ru catalyst and PNN ligand Amides Alkylation [49] Rh catalyst and BINAP ligand Aldehyde Allylation [25] Ir catalyst and P-olefin & amine Aldehydes Allylation [24] Ir catalyst and monodentate phosphine ligand Esters Alkylation [50] Ni catalyst and Mandyphos ligand Amides Acylation [51] Co catalyst and PNP ligand Ketones Alkylation [37] Co catalyst and PN 5 P ligand Amides Esters Alkylation [52] Mn catalyst and PN n P ligand Ketones Alkylation [36,38] Ni catalyst and NNN ligand Amides Esters Alkylation [53] Rh catalyst and NHC ligand Ketones Alkylation [39] Ru(bpy) 3 photocatalyst Aldehydes Alkylation [26,27,30] Ketones Alkylation [40] Imines Alkylation [45] Ir photocatalyst Aldehydes Alkylation [28,29] Catalysts Allylic alkylation and ...…”