Selenium-promoted electrophilic cyclization of arylpropiolamides: synthesis of 3-organoselenyl spiro[4,5]trienones

Abstract

This paper describes a selenium-promoted electrophilic cyclization of arylpropiolamides allowing the synthesis of 3-organoselenyl spiro[4,5]trienones via a 5-endo-dig ipso-mode. The 3-organoselenyl-quinolinone derivative formation via 6-endo-dig was avoided using an electrophilic organoselenium species in a metal-free protocol. The use of phenylselenyl bromide (1.3 equiv.), as the electrophilic source, in nitromethane (3 mL) at 90 °C enabled the cyclization of N-(2-methoxyphenyl)-N-methyl-3-phenylpropiolamides, giving 3-organoselenyl[4,5]triene-2,6-dione derivatives. The extension of the standard conditions to the N-(4-methoxyphenyl)-phenylpropiolamides led to the corresponding 3-organoselenyl spiro[4,5]trienones having the carbonyl group at the 8-position. Besides, we demonstrated a general application of our approach by using 3-organoselenyl spiro[4,5]trienones as substrates in Suzuki cross-coupling reactions, which gave the cross-coupled products in good yields.