Reaction of Benzoyl Chloride with Triphenyltin Hydride

Chemistry of Acyl Radicals

“…The stannane-mediated reduction of acyl chlorides to aldehydes via acyl radicals is plagued by the formation of byproducts, typically esters, which may even become the major products depending on the conditions. Thus, early workers studying the reduction of benzoyl chloride noted the formation of benzyl benzoate and, under certain conditions, its exclusive nature. − There was much discussion about the mechanism of ester formation 109-114 until Ingold and co-workers convincingly demonstrated it to involve over-reduction of the aldehyde by a polar mechanism and reaction of a stannyl alkoxide with the acyl chloride. , In light of these complications, as is evident from sections VII and VIII, studies on the use of acyl radicals generated from acyl chlorides in synthesis are quite limited.…”

“…These latter effects obviously arise from the restriction of conformation imposed by the substituents and are related to the well-known "gem-dimethyl" effect. A combination of a 3-ketal and an allylic ether (111) results in almost quantitative cyclization, but again the endodirecting effect of the allylic ether is noticeable. This directing effect may be overcome by substituting the terminal position of the olefin as in 112.…”

Photochemistry of alkyl halides. 4. 1-Norbornyl, 1-norbornylmethyl, 1- and 2-adamantyl, and 1-octyl bromides and iodides

“…VII, irradiation of the iodide 22a in methanol, ether, or benzene afforded predominantly 1-octene (26), accompanied by octane (24) and a mixture of 2-and 3-octene (27).14 Nucleophilic substitution products were found only in low yields, but, interestingly, usually included both 1-and 2-octyl derivatives.…”

“…Irradiation of either 1-iodonorbornane (la) or 1-iodooctane (22a) in the presence of 1 mol equiv of triethylamine in a variety of solvents resulted in a marked increase in the relative amount of the reduction product norbornane (8) or «-octane (24) formed. The one exception to this was irradiation of 22a in benzene, in which case there was a marked increase in the amount of 1-octene (26) at the apparent expense of the reduction product «-octane (24): Effect of Oxygen. Irradiation of either 1-iodoor 1-bromonorbornane (la or b) in a methanolic solution saturated with oxygen resulted in substantially lower yields of both the substitution product 3a and the reduction product 8 compared with irradiations conducted in the absence of oxygen.…”

Reductive Acylation of Ketones1

“…Reactions, 13, 1 (1963). (6) Migration of an organic group from a quaternary boron atom to an attached, electron-deficient carbon atom is well established, occurring in the reactions of triorganoboranes with carbon monoxide,7 isonitriles,8 and diazomethane.8(7) . E. D. Hillman, J.…”