Nickel-Catalyzed Asymmetric Hydrocyanation of Allenes

Abstract

The first catalytic enantioselective hydrocyanation of allenes catalyzed by a (R,R)-Ph-BPE–Ni­(0) complex catalyst has been accomplished. Numerous optically active allylic nitriles were obtained in good yield with excellent enantioselectivities (up to 98% ee).

Hydroarylation of N‐Allenyl Derivatives Catalyzed by Copper**

“…Hydrofunctionalization of allenes mainly allowed the selective formation of C–N, C–O, and C–C bond. [ 2,3,5–8 ] The latter being performed through the addition of pronucleophiles such as malonates, [ 9–12 ] nitriles, [ 13–16 ] alkynes, [ 17–19 ] alkenes, [ 20–22 ] and aryl derivatives. The reaction of aromatic compounds with allenes, known as hydroarylation reaction, consists of adding an aryl moiety to a C–C double bond and constitutes a powerful tool to form a Csp 3 –Csp 2 bond in a regio‐ and stereoselective manner.…”

Access to 1,3‐Dinitriles by Enantioselective Auto‐tandem Catalysis: Merging Allylic Cyanation with Asymmetric Hydrocyanation

“…Since 1979, various synthetic methods for obtaining chiral nitriles through asymmetric hydrocyanation have been achieved due to the emergence/utilization of wide variety of chiral ligands . However, it should be noted that such strategies are restricted to strained alkenes, vinylarenes, 1,3‐dienes and allenes as prochiral substrates. In 1992, RajanBabu and Casalnuovo developed a Ni‐catalyzed asymmetric hydrocyanation of 2‐methoxy‐6‐vinyl‐naphthalene with sugar‐derived diphosphonite ligand L1 , which led to corresponding nitriles with excellent levels of enantiocontrol .…”

Photo-Promoted Decarboxylative Alkylation of α,β-Unsaturated Carboxylic Acids with ICH2CN for the Synthesis of β,γ-Unsaturated Nitriles

“…The hydrolysis of the cyano group of 2a resulted in the γ , δ -unsaturated carboxylic acid ( 5 ). Then, the epoxidation of the alkene of 2a was successfully carried out using m -CPBA, affording the epoxide ( 6 ) in 65% yield …”