Nickel‐Catalyzed Intramolecular Decarbonylative Coupling of Aryl Selenol Esters

Abstract

This report describes a method for Ni‐catalyzed intramolecular decarbonylative coupling, which enables the conversion of areneselenol esters to diaryl selenides. The inexpensive and readily available catalyst can be employed under mild reaction conditions for the construction of structurally diverse diaryl selenides, including heterocyclic and natural product derivatives.

Palladium-Catalyzed Carbonylative Synthesis of Aryl Selenoesters Using Formic Acid as an Ex Situ CO Source

“…Methyl 4-((Phenylselanyl)carbonyl)benzoate (3ha). 32 Yield: 61% (58.6 mg) (using 12 equiv of H 2 SO 4 and HCOOH); yellowish solid; mp 133.0−134.5 °C; column chromatography (Hex/AcOEt95:5); 1 H NMR (400 MHz, CDCl 3 ): δ 8.15 (d,J = 8.1 Hz,2H),7.98 (d,J = 8.2 Hz,2H),2H),3H), 3.96 (s, 2H); 13 C{ 1 H} NMR (101 MHz,CDCl 3 ): δ 193.4,166.1,141.9,136.4,134.7,130.3,129.6,129.4,127.3,125.6,52.7 ppm. Se-phenyl 3-Cyanobenzoselenoate (3ia). Yield: 52% (44,6 mg) (using 12 equiv of H 2 SO 4 and HCOOH); white solid; mp 90.7−92.1 °C; column chromatography (Hex/AcOEt95:5); 1 H NMR (400 MHz, CDCl 3 ): δ 8.20 (s, 1H), 8.14 (d,J = 7.9 Hz,1H),7.89 (d,J = 7.6 Hz,1H),7.64 (t,J = 7.8 Hz,1H),2H),3H); 13 C{ 1 H} NMR (101 MHz,CDCl 3 ): δ 192.2,139.7,136.8,136.3,131.3,130.9,130.2,129.8,129.7,125.0,117.7,113.7 ppm; HRMS (ESI-TOF) m/z: [M + H] + calcd for C 14 H 9 NOSe, 287.9922; found, 287.9932.…”

Nickel-Сatalyzed Carbon–Selenium Bond Formations under Mild Conditions

“…9 Very recently, Xu, Yu, and coworkers realized the synthesis of various selenides by nickel-catalyzed intramolecular decarbonylative reaction of aryl selenoesters. 10 Also, Shao et al reported a nickel-catalyzed cross-electrophile coupling of aryl iodides and benzeneselenosulfonates 11 (Scheme 1b). These C-Se bond construction methods proceeded mainly under elevated temperature, in the presence of strong bases or stoichiometric amounts of metal reductant.…”