Novel α-arylnitriles synthesis via Ni-catalyzed cross-coupling of α-bromonitriles with arylboronic acids under mild conditions

Abstract

An applicable and easy-handling Ni-catalyst can be used to promote direct arylation of α-bromonitriles with various arylboronic acids to construct α-arylnitriles under mild conditions. The methodology tolerates β-hydrogens and functional groups in the substrates.

Iodine-Catalyzed Radical Oxidative Annulation for the Construction of Dihydrofurans and Indolizines

“…Therefore, a new iodine-catalyzed reaction pathway needs to be explored. With continuous interest in the α-functionalization of carbonyl compounds, we herein communicate our progress in the iodine-catalyzed radical oxidative annulation of β-keto esters or 2-pyridinyl-β-esters with alkenes for synthesizing dihydrofurans and indolizines (Scheme ).…”

Synthesis of 2-(Cyanomethyl)benzoic Esters via Carbon–Carbon Bond Cleavage of Indanones

“…( R f = 0.20, petroleum ether/ethyl acetate = 20/1); 1 H NMR (600 MHz, CDCl 3 ) δ 8.08 (d, J = 7.7 Hz, 1H), 7.58–7.55 (m, 2H), 7.45–7.41 (m, 1H), 4.39 (q, J = 7.1 Hz, 2H), 4.22 (s, 2H), 1.41 (t, J = 7.1 Hz, 3H); 13 C­{ 1 H} NMR (150 MHz, CDCl 3 ) δ 166.3, 133.0, 131.9, 131.5, 130.2, 128.7, 128.3, 118.0, 61.4, 23.2, 14.2. Spectroscopic data matches that reported in the literature …”

“…In 2005, Kunai and co-workers reported an alternative approach taking advantage of aryne insertion into α-cyano esters (Scheme b) . Lei developed an efficient Ni-catalyzed coupling reaction of arylboronic esters with α-bromonitriles in 2011 (Scheme c) . Nevertheless, the synthetic approaches to 2-(cyanomethyl)­benzoic esters are still underdeveloped.…”

Iron-Catalyzed Dehydrogenative sp3–sp2 Coupling via Direct Oxidative C–H Activation of Acetonitrile

“…Most importantly, the (hetero)­arylacetonitrile unit has appeared in several pharmaceutically active molecules, such as levocabastine, verapamil, isoaminile, anastrozole, diphenoxylate, and cilomilast . Therefore, various methods for (hetero)­arylacetonitrile motif installations have been developed, including the nucleophilic substitution of benzyl halides with cyanide (Figure a), the dehydrations of primary amides or aldoximes (Figure b), the nucleophilic substitution of aromatic fluorides followed by decarboxylation (Figure c), and the palladium-catalyzed cross-coupling of aryl halides with functionalized acetonitriles such as bromoacetonitrile, TMS-acetonitrile, Bu 3 Sn-acetonitrile, and cyanoacetate salts (Figure d) . These strategies are effective for assembling (hetero)­arylacetonitriles, though they sometimes suffer from poor reaction atom-economy and the requisition of toxic transition metal catalysts or harsh conditions.…”