A series of cyclohexyl‐fused SPINOL‐derived phosphoric acids (Cy‐SPA) have been developed to catalyze the kinetic resolution of 2‐N‐acylamido tertiary allylic alcohols, providing access to chiral oxazolines bearing C‐2 alkyl substituents with high enantioselectivities (with s‐factors up to 153). Gram‐scale reaction with 1 mol% catalyst loading and transformations of the chiral products demonstrates the value of these methods.
Herein, we report the asymmetric synthesis of chiral azides possessing an α-quaternary stereocenter via chiral phosphoric acid catalysed direct enantioselective Mannich reactions of α-azido cyclic ketones with aldimines.
Asymmetric functionalizations of α‐sulfanyl cyclic ketones were realized via chiral phosphoric acid catalyzed enantioselective addition reactions with aldimines, azodicarboxylates and allenamides. A series of chiral organosulfur compounds possessing sulfur‐containing tetrasubstituted stereocenters were accessed via these methods, with excellent regioselectivities and high stereoselectivities.magnified image
A practical
method for kinetic resolution of α-tertiary propargylic
amines has been achieved via asymmetric remote aminations of anilines
with azodicarboxylates enabled by chiral phosphoric acid catalysis.
A broad range of aryl and alkyl groups at the α-position, as
well as the substituted alkynyl and N-aryl groups
were well tolerated in these reactions, providing high kinetic resolution
performances (with an s-factor up to 111). In addition,
the α-tertiary amines bearing an α-CN group (the Strecker
reaction product) could be kinetically resolved with excellent stereoselectivity
as well under the same reaction conditions. Fruitful transformations
of the chiral amination products and the recovered propargylic amines
demonstrated the power of this method in asymmetric synthesis of α-tertiary
amines and their derivatives.
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