Cycloalkanes from amines

Thermochemical data from the compilation of Stull et at., 1969. Entropy values are based on a 1 M standard state. The asterisk denotes symmetry-corrected quantities. Symmetry numbers were chosen as follows 18 for the n-alkanes, cis-3-hexene, dibuthyl sulphide, diethyl ether, and diethyl amine 2n for the cycloalkanes and 2 for all of the remaining ring compounds 3 for the alkanols, alkanethiols and alkyl amines 9 for the methyl alkyl sulphides... 

Metal nitrene complexes were used in a number of C-H amination reactions (recent reviews [358, 359]). Copper ketiminate complexes react with azides to nitrene complexes, which were isolated [360]. (p-Ketiminate)copper(I) complex 262 (2.5 mol%) serves therefore as an efficient catalyst for the intermolecular C-H amination of alkylarenes, cycloalkanes, or benzaldehydes 260 using adamantyl azide 261 as the nitrogen source ig. 68) [361]. The corresponding adamantyl amines or amides 263 were isolated in 80-93% yield. Copper complex 262 forms initially a dinuclear bridged complex with 261. From this a copper nitrene complex is generated by elimination of nitrogen, which mediates the hydrogen abstraction from 260. 

On this ground, DCA was found a suitable sensitizer to induce the photooxygenation of a great variety of organic compounds such as alkenes [84,94-98], alkynes [99,100], sulfides [84,98,101], dienes [84], sulfoxides [102], cycloalkanes [103,104], cycloalkenes [105,106], epoxides [107,108], aziridines [109], allenes [110], dioxenes [111], p-dioxins [111,112], aromatic substrates [113], tertiary amines [114], and of great interest from the mechanistic point of view, sterically hindered olefines [97,115-117]. 

From To - Alkanes Cycloalkanes Alkenes Alkynes Aryls Halogen compounds Alcohols Phenols Ethers, Quinones B. and Si compounds P and 6i compounds Nitro, Nitroso, Azo, Azoxy, Hydrazo, ides Amines Organometallic Aldehydes Ketones Acids, Anhydrides, Esters Arn.des, Amidines, Nitriles Hydroky-aldehydes Amino Heterocycles Nucleosides Miscellaneous, including heterocycles... 

Photoexcited aromatic hydrocarbons undergo hydrogen abstraction and 1,4-addition reactions with cycloalkanes and hydroxylic compounds. These reactions are believed to take place through an excited singlet state of arene to form an exciplex or ion pair as an intermediate, which on back electron transfer dissociates into triplet diradical and undergoes proton abstraction from solvent or amines, followed by addition of an alkyl or aryl unit to give the products [37]. The following examples of this reaction are illustrative ... 

Silver carbonate-on-Gelite has been recommended for the oxidation of alcohols to aldehydes and ketones. It does not attack hindered hydroxyl groups Prim, amines can be converted to ketones under mild conditions through prototropic isomerization of certain Schiff bases A variety of aldehydes, including deu-terio-, a, -ethylene-, and cycloalkane-aldehydes have been obtained in a novel manner from dihydro-1,3-oxazines Non-con-... 

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