Decanning Decarbonylation

It is noteworthy that irradiation of tetracyclo[6.2.0.0 . 0 ]decan-9-one resulted in cycloreversion and formation of ketene and vinylcyclopropane tricyclo[5.1.0.0 ]oct-5-ene instead of ring cleavage and decarbonylation. A C-C double bond a to a cyclopropane ring also resulted when spiro bicyclo[2.2.1]hept-5-ene-7,l -cyclopropane -2-one eni/o-epoxide underwent a deep-seated rearrangement upon irradiation through Corex to give 5-oxo-spiro[2.4]hept-6-ene-4-ylacetaldehyde in 50% yield. ... 

The intramolecular hydroacylation of aldehydic olefins is catalyzed by cationic Rh complexes of chelating phosphines in polar nonprotic solvents. The rate decreases with increasing substrate Rh ratio since the substrate complex with the catalyst inhibits the reaction. However, since this complexation also prevents the decarbonylation of the aldehyde, catalyst deactivation decreases, leading to a higher turnover. The only effective catalytic C—H activations are carried out with [RhCl(CO)(PMe3)2] under photolysis which removes CO. Alkanes are converted to alkenes in the order cyclooctane > cyclohexane > n-decane n-hexane. Up to 200 turnovers cyclooctane per hour are observed. In order to generate terminal... 

Alkanes are a desirable fuel compound as they have fuel properties nearly identical to that of gasoline. Production of a range of alkanes including nonane and decane has been shown inf. coli [102]. Fatty acyl-ACPs (AGP = acyl carrier protein) were produced through the fatty acid biosynthetic pathway. They were then reduced to aldehydes and decarbonylated to alkanes by an exogenous enzyme, CERl from A. thaliana. 

Meerwin s ester has been used as a starting point for the synthesis of 3,7-disub-stituted bicyclo[3,3,2]decanes. Thus, the homoadamantanedione dicarboxylic acid (677) was prepared by standard methods and converted into (678) by sequential Wolff-Kishner reduction and decarbonylation of the bis-acid chloride with catalytic chlorocarbonylbis(triphenylphosphine)rhodium. Fragmentation of (678) with aqueous alkali gave (679). 

Aldehydes undergo a decarbonylation reaction by action of a transition metal complex [17]. For example, benzaldehyde was decarbonylated with Wilkinson complex to furnish benzene along with a rhodium carbonyl complex 47 (Scheme 7.14) [17e,f]. Oxidative addition of the aldehydic C-H bond to rhodium, migratory deinsertion of CO, and reductive elimination operate in sequence for the decarbonylation reaction. Decanal was also decarbonylated to furnish a mixture of nonane and nonene, which were produced via the alkylpalladium intermediate 48 (Scheme 7.15) [17d]. 

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