Practical approach for asymmetric hydroxyamination of aldehydes with in situ generated nitrosocarbonyl compounds: application to one-pot synthesis of chiral allylamines.

The highly regio- and enantioselective hydroxyamination of aldehydes with in situ generated nitrosocarbonyl compounds from a hydroxamic acid derivative was realized by simple and readily available chiral amine catalysts. The resulting hydroxyamination products were readily converted to the corresponding chiral 1,2-aminoalcohol or allylamine derivatives in one pot.

Metal-free enantioselective hydroxyamination of aldehydes with nitrosocarbonyl compounds catalyzed by an axially chiral amine.

The first example of a highly regio- and enantioselective hydroxyamination of aldehydes with in situ generated nitrosocarbonyl compounds from hydroxamic acid derivatives was realized by combined use of TEMPO and BPO as the oxidant in the presence of a binaphthyl-modified amine catalyst.

Powerful amino diol catalyst for effecting the direct asymmetric conjugate addition of aldehydes to acrylates.

Di-tert-butyl methylenemalonate (1) could be employed as a reactive equivalent of a three-carbon Michael acceptor such as acrylate in a direct asymmetric conjugate addition of aldehydes catalyzed by an axially chiral amino diol (S)-3a. Furthermore, acrylate, an unexplored and challenging substrate in enamine catalysis, has also been successfully employed in asymmetric conjugate addition reaction. Relatively inert acrylate is doubly activated by polyfluoroalkyl group of 2 and the hydroxyl group on the axially chiral amino diol catalyst (S)-3b, giving corresponding conjugate adducts in high yield with excellent enantiomeric excess.

Direct asymmetric bromination of aldehydes catalyzed by a binaphthyl-based secondary amine: highly enantio- and diastereoselective one-pot synthesis of bromohydrins.

One-pot stereoselective synthesis of bromohydrins as a useful chiral building block was achieved by the reaction of Grignard reagents with optically active α-bromoaldehydes, which were in situ generated by direct asymmetric bromination of aldehydes catalyzed by a binaphthyl-based secondary amine (S)-3.

Palladium-catalyzed asymmetric decarboxylative lactamization of gamma-methylidene-delta-valerolactones with isocyanates: conversion of racemic lactones to enantioenriched lactams.

A palladium-catalyzed asymmetric decarboxylative reaction of racemic gamma-methylidene-delta-valerolactones with aryl isocyanates has been developed to give enantioenriched 3,3-disubstituted 2-piperidones. High enantioselectivity has been achieved by tuning the ester group on substrate and the substituents of phosphoramidite ligand.