Deoxygenation and Desulfurization of Organic Compounds via Transition Metal Atom Cocondensation

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(?;6-dibenzyl ether)chromium(O) 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.