2- bicyclo octan-3- alkanal

Dehydrocyclizatlon Pt(0) can be used for dehydrogenation of alkanes to alkenes. Ti(0) is known to absorb H2 to form a dihydride. Paquette et al.1 reasoned that a combination of the two metals could in principal effect dehydrocyclization. Indeed, cyclooctane when heated with Pt(0) and Ti(0) (1 1) adsorbed in A1203 is converted into bicyclo[3.3.0]octane (equation I). 

A route to bicyclic alkanes was published by Ley et al. [31], which involved a double Michael addition with a resin-bound unsaturated ester to afford the highly functionalized bicyclo[2.2.2]octane(Fig. 5). 

Recently, Rooney and co-workers (23,58,59) have questioned the view that triadsorption by loss of 3 hydrogen atoms from the alkane is the minimum requirement for bond-shift reactions. They studied the isomerization of a series of caged hydrocarbons in excess hydrogen on palladium and platinum catalysts. The compounds were chosen in order to render difficult or totally exclude a mechanism involving aory-triadsorbed species. Thus, l,7,7-trimethyl[2,2,l]-heptane interconverts with its endo- and exo-2,3,3-trimethyl isomers, bicyclo-[3,2,2] octane changes to bicyclo[3,3,l] nonane, and protoadamantane to... 

The name of a bicyclic compound is based on the name of the alkane having the same number of carbons as there are in the ring system. This name follows the prefix bicyclo and a set of brackets enclosing three numbers. The following examples contain eight carbon atoms and are named bicyclo[4.2.0]octane and bicyclo[3.2.1]octane, respectively. 

Many bicycloalkanes are as unreactive as alkanes or unstrained cycloalkanes. They have very high values and their low electron affinities make them poor electron acceptors. The ionization potentials of unstrained bicycloalkanes are somewhat lower than those of unstrained cycloalkanes—bicyclo[2.2.2]octane IP 9.47 eV), bicyclo[4.3.0]nonane [IP 9.46 eV), or bicyclo[4.4.0]decane [IP 9.32 eV) lie below the 9.75-9.90 eV range characteristic of cycloalkanes [5]. As a result, they are somewhat easier to oxidize in solution or in solid matrices. Strained bicycloalkanes have even lower ionization potentials (bicyclo] 1.1. Ojbutane, IP 8.7 eV) the ring strain... 

Furthermore, di- and polychlorination are much less prevalent. Dicarboxylic acids are predominantly chlorinated in the middle of the chain, and adamantane and bicyclo[2.2.2]octane at the bridgeheads by this procedure. The reasons for the high co - 1 specificity are not clearly understood. Alkyl bromides can be regioselectively chlorinated one carbon away from the bromine (to give vic-bromochlorides) by treatment with PCls. Alkyl chlorides can be converted to vic-dichlorides by treatment with Mods. " Enhanced selectivity at a terminal position of w-alkanes has been achieved by absorbing the substrate onto a pentasil zeolite. In another regioselective chlorination, alkanesulfonamides... 

With bridgehead substituted bicyclo[4,2.0]alkanes, each pair of cis- or /ran.v-fused systems gives essentially the same ratio of products. Thus, solvolysis of cis- and m 5-l-(3,5-dinitrophenyl-methoxy)bicyclo[4.2.0]octane in 80% aqueous acetone buffered with 2,6-lutidine at 140°C and 100°C, respectively, gave the same mixture of spiro[2.5]octan-4-ol 14 and bicyclo[4.2.0]octan-l-ol 13 obtained from spirocyclopropylmethyl cation derivatives, suggesting one or more common intermediates. ... 

Polymerization of Bicyclo[n. 1.0]Alkanes. From the large-ring bicyclo[n.l.0]alkane series, six were chosen because of their relative ease of synthesis bicyclo[5.1.0]octane (M2), bicyclo[6.1.0]nonane (M3), bicyclo[ 10.1.0] tridecane (M4), and the corresponding 1-methylbicyclo-[n. 1.0] alkanes and prepared from the corresponding cycloalkenes or 1-methylcyclqalkenes (cycloheptene, cyclooctene, and cyclododecene). See Equation 4. 

Bridged bicyclic alkanes are named in the manner bicyclo[numberMumber,number] alkane. As illustrated for bicyclo[3.2.1]octane, the parent alkane is the one with the same number of carbons as the total in the bicyclic skeleton. 

In Table 6, which was compiled from work on bicyclo[n.l.O]alkanes, bicyclo[1.1.0]-butanes, bicyclo[2.1.0]hexanes, bicyclo[2.2.1]heptanes , bicyclo[3.1.1]heptanes bicyclo[2.2.2]octanes ", bicyclo[3.3.0]octanes", bicyclo[4.n.0]alkanes, bicyclo[3.3.13-nonanes" spiro[4.5]alkanes" and trans-decalins the chemical shifts of several bicyclic alkanes are tabulated. The values were mainly explained by the steric effects present in the different structural environments, with the exception of fused cyclopropane rings (see below). 

---