Cu(TFA)₂‐Catalyzed Picolinamido‐Directed C(sp²)−H Cyanation of Naphthalenes by Using Benzoyl Cyanide as a Cyano Source

Abstract

Ap rotocol for the Cu(TFA) 2 -catalyzed( TFA = trifluoroacetic acid) picolinamido-directedC 8 ÀHc yanation of naphthalene derivatives with benzoyl cyanide as the cyano source has been developed. As eries of 8-cyano-1-(picolinamido)naphthalene derivatives were efficiently obtained in moderate to good yields by using this method. We prepared at otal of 22 products, 10 of which have not previously been reported. Benzoyl cyanide was originally employed for the C(sp 2 )ÀHc yanation of arenes. The picolinamide moiety served ac riticalr olea st he directing group in this cyanation reactionofnaphthalenes.

Copper Mediated Chemo‐ and Stereoselective Cyanation Reactions

“…In the reaction, the picolinamide moiety was the critical directing groups forthe cyanation reaction of naphthalenes (See Figure 114). [119] …”

“…In the reaction, the picolinamide moiety was the critical directing groups forthe cyanation reaction of naphthalenes (See Figure 114). [119] Copper-based catalytic material (CuBr or Cu(MeCN) 4 PF 6 ) promoted cycloketone oxidation via chemodivergent radical mediated CÀ C bond cleavage under redox neutral conditions to γand δ-alkoxylated, alkoxylated, and hydroxylated nitriles. Cu(MeCN) 4 /PF 6 /t-BuXPhos/R 3 OH based catalyzed system yielded γand δ-alkoxylated product from the same substrate,whereas R 3 OH was replaced with (CH 3 ) 2 NCO as substrate for the synthesis of hydroxylated nitriles as the major product.…”

Recent Advances in Copper(II)-Mediated or -Catalyzed C–H Functionalization

“…Sun, Chu and co-workers described a reaction protocol for the copper-catalyzed cyanation of 1-aminonaphthalenes with benzoyl cyanide as the cyano source (Scheme 13). 19 The N-(2-pyridyl)carboxamide moiety was employed as a bidentate directing group. A series of 8-cyano-N-(2pyridyl)naphthalene-1-carboxamide derivatives was synthesized in moderate to good yields.…”

Catalyst‐free straightforward synthesis of 3‐cyano‐3‐arylamino‐2‐oxindoles through hydrocyanation with benzoyl cyanide

“…Benzoyl cyanide is less toxic cyanating agent, which can be easily prepared by reaction of commercial available benzoyl chloride and nontoxic potassium hexacyanoferrate (II) . In recent years, benzoyl cyanide has been reported to act as cyanating agent for terminal alkynes, 3‐arylideneindolin‐2‐ones, naphthalenes, tertiary amines, and aromatic bromides . However, the reports about benzoyl cyanide as a hydrocyanating agent were scarce; only the hydrocyanation of aldehydes was reported …”