1- Adamantanecarbonyl chloride

Reduction of 1-adamantanecarbonyl chloride at carbon or mercury leads to the quantitative formation of 1-adamantanecarboxaldehyde [80]. Mubarak [81] investigated the reduction of 2-thiophenecarbonyl chloride at both carbon and mercury the starting material appears to undergo a two-electron reduction to form an acyl anion, which leads to l,2-di(2-thienyl)ethene-l,2-diol di(2-thiophenecarboxylate) as the major product and to 2-thiophenecarboxaldehyde as the minor product. 

Under free-radical conditions, the reaction of (TMS)3SiH with acid chlorides, RC(0)C1, gives the corresponding aldehydes and/or the decarbonylation products depending on the nature of substituent R [42]. The reduction of 1-adamantanecarbonyl chloride is given in Reaction (4.19). 

Adamantanecarbonyl fluoride (25) required for 13CNMR investigation is conveniently prepared by refluxing the 1 -adamantanecarbonyl chloride (24) with sodium fluoride in acetonitrile for 12 hours.22 Similarly the 1,3-adamantanedicarbonyl fluoride is also prepared from the corresponding dichloride.22... 

Quantitative conversion of 1-adamantanecarbonyl chloride to 1-adamantanecarbox-aldehyde has been accomplished by reduction of the acyl halide at carbon and mercury in MeCN containing TEAP [227]. Lozano and Barba [228] reduced 2-chloro-2-phenylacetyl chloride at mercury in methylene chloride containing TEACl and obtained derivatives of pyran-2-one and pyran-4-one. In subsequent work [229,230], these authors investigated the reduction of 2-bromo-2,2-diphenylacetyl bromide at graphite in methylene chloride containing TEABr and in the presence of inorganic sulfur compounds in the first study, a new sulfurated heterocyclic product was obtained ... 

The acylpalladium complex formed from acyl halides undergoes intramolecular alkene insertion. 2,5-Hexadienoyl chloride (894) is converted into phenol in its attempted Rosenmund reduction[759]. The reaction is explained by the oxidative addition, intramolecular alkene insertion to generate 895, and / -elimination. Chloroformate will be a useful compound for the preparation of a, /3-unsaturated esters if its oxidative addition and alkene insertion are possible. An intramolecular version is known, namely homoallylic chloroformates are converted into a-methylene-7-butyrolactones in moderate yields[760]. As another example, the homoallylic chloroformamide 896 is converted into the q-methylene- -butyrolactams 897 and 898[761]. An intermolecular version of alkene insertion into acyl chlorides is known only with bridgehead acid chlorides. Adamantanecarbonyl chloride (899) reacts with acrylonitrile to give the unsaturated ketone 900[762],... 

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