SN2 DISPLACEMENTS AND REDUCTIVE COUPLING OF KETONES WITH OLEFINS IN N,N-DIETHYLACETAMIDE AND N-ETHYLPYRROLIDONE

N-Diethylacetamide (DEA) and N-ethylpyrrolidone (NEP) are complementary to hexamethylphosphoric triamide (HMPA), dimethylformamide, and dimethyl sulfoxide as solvents in which to carry out several reactions commonly conducted in polar, aprotic media. Reaction of neopentyl tosylatss with lithium halides in DEA and NEP gives good yields of neopentyl halides. Ketones and terminal olefins are reductively coupled to tertiary alcohols in fair to good yields in mixtures containing NEP, sodium, and (tert-butyl alcohol; l-hepten-6-one and l-octen-7-one are cleanly cyclized to five-and six-membered rings, respectively, in good yield by this same mixture. Terminal olefins are reduced to alkanes in fair yield by DEA-sodium-tert-butyl alcohol mixtures; di-and tetrasubstituted olefins are resistant to reduction by this mixture. © 1979, American Chemical Society. All rights reserved.