Iridium‐Catalyzed α‐Alkylation of Arylacetonitriles Using Secondary and Primary Alcohols

Abstract

In the presence of NaOtBu, [Cp*IrCl2]2‐catalyzed reaction of arylacetonitriles with secondary alcohols was performed to yield α‐monoalkylation products of arylacetonitriles. The catalyst and conditions also suited for the α‐monoalkylation of arylacetonitriles with primary alcohols.

Nickel-Catalyzed α-Alkylation of Arylacetonitriles with Challenging Secondary Alcohols

“…It should be noted that most of the previous studies also reported toluene as the reaction medium. 21,22 Scheme 1. α-Alkylation of Arylacetonitriles with Secondary Alcohols Thereafter, we attempted to expand the substrate scope (Scheme 3). At first, cyclohexanol was reacted with various arylacetonitriles.…”

“…). 21 The crude product was purified by column chromatography [silica as the stationary phase and a mixture of hexanes and ethylacetate (9.7:0.3) as the eluent] to give pure product P 31 as a colorless oil (0.171 g, 75%). 1 H NMR (400 MHz, CDCl 3 ): δ 7.19 (d, J = 8 Hz, 2H), 6.89 (d, J = 8 Hz, 2H), 3.81 (s, 3H), 3.57 (d, J = 7 Hz, 1H), 1.91−1.62 (m, 6H), 1.25−1.08 (m, 5H).…”

“…The very first report was published by Wang and Kong, who used Cp*IrCl 2 . 21 Within few days, Sundararaju et al reported cobalt-catalyzed αalkylation of arylacetonitriles with secondary alcohols. 22 We published the latest report, and a dimeric iridium(III) complex was employed as a very effective catalyst.…”

Ni2P Nanoparticles Supported on N, P Co-Doped Carbon as Catalyst for α-Alkylation of Arylacetonitriles with Alcohols

“…Up to now, several homogeneous and heterogeneous catalysts have been reported for this organic transformation (Scheme ). However, these catalysts require expensive and rare metals like Ru, − Rh, − Ir, − Os, Pd, and Ag . In addition, the examples of alkylation by transition metals complex catalysts, including Mn, − Fe, , Co, − and Ni − also have been documented, but these need multistep ligand synthesis and the addition of bases.…”

Catalytic Formal Conjugate Addition: Direct Synthesis of δ-Hydroxynitriles from Nitriles and Allylic Alcohols

“…Our group demonstrated Ru-macho ( 1a )-catalyzed selective α-alkylation and α-olefination of nitrile compounds by primary and secondary alcohols, in which the reactions proceeded through borrowing hydrogen (BH) and acceptorless dehydrogenative coupling (ADC) pathways, respectively (Scheme b,c). , Notably, various transition-metal catalysts are also reported for the α-alkylation − and α-olefination of nitriles using alcohols (Scheme b,c). Selective cross-coupling of secondary alcohols to β-disubstituted ketones, , α-alkylation of ketones, ketazines synthesis using secondary alcohols, N,N-dialkylation of acylhydrazides using both primary and secondary alcohols, and regioselective hydrogenation of epoxides to secondary alcohols catalyzed by 1a have been reported .…”