Deoxygenation and Desulfurization of Organic Compounds via Transition Metal Atom Cocondensation

Article abstract of DOI:10.1021/jo01303a023

Reactions resulting from the cocondensation of transition metal atoms with a variety of oxygen- and sulfur-containing organic compounds are surveyed.Alkenes are the major or exclusive volatile products when epoxides are reacted with Ti, V, Cr, Co, and Ni atoms. 2,6-Dimethylpyridine-N-oxide and dimethyl sulfoxide undergo deoxygenation upon cocondensation with chromium, but diisopropyl ether and decyl methyl ether do not.Dibenzyl ether yields bis(η⁶-dibenzyl ether)chromium(0) with Cr atoms, but dibenzyl sulfide undergoes desulfurization.Cyclohexanone and cycloheptanone afford low yields of reductive coupling and aldol products when cocondensed with Cr, Co, and Ni atoms.Nitro- and nitrosoarenes are deoxygenated to coupled azo and azoxy products with Cr atoms.Carbazole (3) is obtained from 2-nitrosobiphenyl, implicating nitrene or nitrenoid intermediates.Whereas isocyanides are not formed from isocyanates and metal atoms, they are produced when isothiocyanates are cocondensed with Cr and V atoms.