Catalytic Asymmetric Synthesis of Secondary Nitriles via Stereoconvergent Negishi Arylations and Alkenylations of Racemic α-Bromonitriles
- Catalytic Asymmetric Synthesis of Secondary Nitriles via Stereoconvergent Negishi Arylations and Alkenylations of Racemic α-Bromonitriles
- 최준원; Gregory C. Fu
- Issue Date
- Journal of the American Chemical Society
- VOL 134, NO 22-9105
- The first method for the stereoconvergent cross-coupling of racemic alpha-halonitriles is described, specifically, nickel-catalyzed Negishi arylations and alkenylations that furnish an array of enantioenriched alpha-arylnitriles and allylic nitriles, respectively. Noteworthy features of this investigation include: the highly enantioselective synthesis of alpha-alkyl-alpha-aryl nitriles that bear secondary alpha-alkyl substituents; the first examples of the use of allcenylzinc reagents in stereoconvergent Negishi reactions of alkyl electrophiles; demonstration of the utility of a new family of ligands for asymmetric Negishi crosscouplings (a bidentate bis(oxazoline), rather than a tridentate pybox); in the case of arylzinc reagents, carbon-carbon bond formation at a remarkably low temperature (-78 degrees C), the lowest reported to date for an enantioselective cross-coupling of an alkyl electrophile; a mechanistic dichotomy between Negishi reactions of an unactivated versus an activated secondary alkyl bromide.
- Appears in Collections:
- KIST Publication > Article
- Files in This Item:
There are no files associated with this item.
- RIS (EndNote)
- XLS (Excel)
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.