Catalytic hydrocondensation of carbon monoxide with olefins

New synthetic reactions. Geminal and reductive alkylations

“…Hydrolysis of Methyl l-(2',2'-Dimethoxyethyl)cyclohexane-lcarboxylate to Methyl l-(2'-Oxoethyl)cyclohexane-l-carboxylate (23). A solution of methyl l-(2',2'-dimethoxyethyl)cyclohexane-lcarboxylate (90 mg, 0.391 mmol) in 10 ml of a 1:1 v/v mixture of dioxane and water was treated with 5 drops of concentrated aqueous hydrochloric acid.…”

“…The mixture was washed with 2 X 50 ml of water and subsequently the ether layer separated, dried over anhydrous magnesium sulfate, and evaporated in vacuo to yield 69.0 mg (96%) of an oil whose purity was established by TLC (10% ether in hexane), and whose spectral properties assign the structure methyl l-(2'oxoethyl)cyclohexane-l-carboxylate: ir (CCI4) 2732, 1724 (broad) cm"1; NMR (CC14) 1.44 (bs, 8 ), 2.0 (m, 2 ), 2.50 (d, J = 2.0 Hz, 2 H), 3.68 (s, 3 H), 9.63 (t, J = 2.0 Hz, 1 H); MS m/e (rel %) 184 (0.27), 156 (14), 141 (40), 125 (11), 124 (10), 113 (19), 96 (25), 81 (100), 74 (61), 55 (40); mol wt 184.11004 (caled for C,0H,6O3, 184.10994). Decarbonylation of Methyl l-(2'-Oxoethyl)cyclohexane-l-carboxylate (23). A solution of 23 (41.1 mg, 0.223 mmol) and tris(triphenylphosphine)rhodium chloride16 (212 mg, 0.23 mmol) in acetonitrile (6 ml) was refluxed for 5 hr.…”