Organocatalytic Asymmetric Decarboxylative Amination of ß-Keto Acids: Access to Optically Active α-Amino Ketones and 1,2-Amino Alcohols.

An organocatalytic asymmetric decarboxylative amination reaction of ß-keto acids is described. Under mild reaction conditions, a series of chiral α-amino ketones were obtained in good to high yields (up to 99%) and enantioselectivities (up to 95% ee). A chiral 1,2-amino alcohol was synthesized from the corresponding decarboxylative amination product in several steps without loss of enantioselectivity.

Catalytic Asymmetric Decarboxylative Mannich Reaction of Malonic Acid Half Esters with Cyclic Aldimines: Access to Chiral ß-Amino Esters and Chroman-4-amines.

An enantioselective decarboxylative Mannich reaction of malonic acid half esters (MAHEs) with cyclic aldimines has been accomplished by employing the copper(I)/(R,R)-Ph-Box complex as chiral catalyst. The desired ß-amino esters were obtained in good to high yields with excellent enantioselectivities. Furthermore, one of the corresponding Mannich products could be readily transformed into chiral chroman-4-amines without loss of enantioselectivity, which is a key intermediate of the human Bradykinin B1 receptor antagonist.

Stereoselective Synthesis of Fused Aziridines via One-Pot Sequential Decarboxylative Mannich Reaction and Oxidative C-H Amination of Cyclic Imines with ß-Ketoacids.

A novel one-pot sequential transformation via decarboxylative Mannich reaction (DMR) and oxidative C-H amination of cyclic imines with ß-ketoacids is described. This methodology has been utilized to provide access to fused aziridines with excellent diastereoselectivity. Several examples of catalytic enantioselective sequential transformation are presented.

Cyclic aldimines as superior electrophiles for Cu-catalyzed decarboxylative Mannich reaction of ß-ketoacids with a broad scope and high enantioselectivity.

A novel Cu-catalyzed enantioselective decarboxylative Mannich reaction of cyclic aldimines with ß-ketoacids is described. The cyclic structure of these aldimines, in which the C═N bond is constrained in the Z geometry, appears to be important, allowing Mannich condensation to proceed in high yields with excellent enantioselectivities. A chiral chroman-4-amine was synthesized from the decarboxylative Mannich product in several steps without loss of enantioselectivity.

Catalytic enantioselective addition of terminal 1,3-diynes to N-sulfonyl aldimines: access to chiral diynylated carbinamines.

An efficient method for the asymmetric synthesis of chiral diynylated carbinamines is described. The direct catalytic enantioselective addition of terminal 1,3-diynes to N-sulfonyl aldimines proceeded smoothly under mild reaction conditions to produce diynylated carbinamines in up to 98% yield and 99% ee.