We report the first catalytic asymmetric cyanation of N-Boc ketoimines, which enables highly enantioselective synthesis of oxindole based α-amino nitriles. An unprecedented tandem aza-Wittig/Strecker reaction is also developed, emerging as a promising strategy for the catalytic asymmetric cyanation of ketoimines formed in situ from achiral ketones.

A simple, rapid and efficient practical method for one-pot synthesis of α-amino nitriles has been achieved by a threecomponent condensation of carbonyl compounds, amines and trimethylsilyl cyanide in the presence of p-toluenesulfonic acid (p-TsOH) as a catalyst at ambient temperature. Operational simplicity, economic consideration, high yield, short reaction time and low toxicity are the key fe...

We reveal here the unique reactivity of α-(alkylideneamino)nitriles toward molecular oxygen. Thus, α-(alkylideneamino)nitriles can serve as the imide building block for the efficient synthesis of imides in the absence of transition metals under extremely mild conditions.

2-Tosylacetonitrile (1) when reacted with α,β-unsaturated nitriles 2a-c or a mixture of formaldehyde and 3-amino-2-substituted-pent-2-endinitriles 6a,b yielded pyridine derivatives 3a-c and 9a,b, respectively, while when subjected to react with salicylaldehyde yielded chromene derivatives 4 and 5, subsequently. The behavior of thiocarbamoyl derivative 10 derived from 1 towards some α-halogenate...

Azides and nitriles are important building blocks for the synthesis of nitrogen-containing bioactive compounds. The first example of enantioselective palladium-catalyzed decarboxylative allylation of α-azido and cyano β-ketoesters is reported. Indanone derivatives were obtained in 50-88% yield/77-97% ee and 46-98% yield/78-93% ee for azide and nitrile substituents, respectively. The required st...

An efficient catalytic route for the synthesis of α,β-unsaturated nitriles from easily accessible gem-dibromoolefins has been developed. The method utilized inexpensive reagents such as Cu2O as a catalyst, L-proline as a ligand and NaCN as a cyanide source to afford α,β-unsaturated nitriles in high yields (62-86%). A deuterium exchange study has shown that one of the bromide atoms of gem-dibrom...

Novel routes for the preparation of 2-amino-4H-pyran-3-carbonitrile 9, amino-arylbenzoic acid ester derivatives 13a,b, 2-aminotetrahydro-4H-chromene-3-carbonitrile 18, 3-amino-4-cyanotetrahydronaphthalene-2-carboxylic acid ester 26 and 4-amino-3,5-dicyanophthalic acid ester derivatives 37a-c were developed. The synthetic methods utilize one-pot reactions of acetylene carboxylic acid esters, α,β...

Palladium-catalyzed synthesis of nitriles from amides has been described. Two similar, but complementary reaction conditions have been identified to convert various amides including α,β,γ,δ-unsaturated amides, cinnamides, aromatic amides and alkyl amides to the corresponding nitriles in good to excellent yield.