Cyclic alkenes, hydrogenation

As mentioned in Section 3.2, hydrogenation is by far the most investigated catalytic reaction and palladium the most commonly employed metal, followed by platinum. The most common substrates for catalytic hydrogenation tests are simple alkenes, cyclic alkenes and unsaturated carbonylic compounds. In the latter case, conjugated substrates (a,P-unsaturated aldehydes, acrylic acid) have received particular attention. 

Although transition metal-mediated P-H addition across ordinary alkenes proceeds well only with five-membered cyclic hydrogen phosphonates, addition across the olefinic linkage of a,P-unsaturated compounds occurs readily with a range of phosphorus species and catalytic agents. Of particular note are the reaction systems involving platinum,96-107 palladium,108-115 and the lanthanides.116-122... 

Han, L.-B., Mirzaei, F., Zhao, C.-Q., and Tanaka, M., High reactivity of a five-membered cyclic hydrogen phosphonate leading to development of facile palladium-catalyzed hydrophosphorylation of alkenes, /. Am. Chem. Soc., 122, 5407, 2000. 

Cyclic Alkenes. The directing effect of alcohol substituents is perhaps most dramatically demonstrated with cyclic alkenes in which products are formed via hydrogenation from the more hindered face (Table 1). Entries 1-3 serve to illustrate that the directing alcohol may reside in either the allylic, homoallylic, or bis(homoallylic) position relative to the alkene undergoing hydrogenation, while synthetically useful levels of selectivity are retained. Entry 4 is included to illustrate the dramatic steric congestion which can be overcome in directed hydrogenation... 

Hunsdiecker reaction, 341 Hybridization, 17 Hybrid orbital number, 17, 18, 32 Hybrid, resonance, 24 Hydration of cyclohexane derivatives, 191 Hydrazine, 4 Hydride shift, 93 Hydroboration, 95 Hydroboration-oxidation, 258, 270 Hydrocarbons, cyclic, 162 unsaturated, 87 Hydrogenation of alkenes, 57 Hydrogen bond, 22 Hydroperoxides in ethers, 284 Hydroquinone, 430 Hydroxy acids, 344... 

Stereochemical features in the oxidative addition and the elimination of /3-hydrogen of cyclic and acyclic alkenes are different. The insertion (palladation) is syn addition. The syn addition (carbopalladation) of R—Pd—X to an acyclic alkene is followed by the syn elimination of 3-hydrogen to give the trans-a ksne 6, because free rotation of 5 is possible with the acyclic alkene. On the other hand, no rotation of the intermediate 7 is possible with a cyclic alkene and the syn elimination of /3-hydrogen gives the allylic compound 8 rather than a substituted alkene. 

The bond highlighted m yellow is the peptide bond ) Pencyclic reaction (Section 10 12) A reaction that proceeds through a cyclic transition state Period (Section 1 1) A honzontal row of the penodic table Peroxide (Section 6 8) A compound of the type ROOR Peroxide effect (Section 6 8) Reversal of regioselectivity oh served m the addition of hydrogen bromide to alkenes brought about by the presence of peroxides m the reaction mixture... 

The stereochemistry of radical addition of hydrogen bromide to alkenes has been studied with both acyclic and cyclic alkenes. Anti addition is favored.This is contrary to what would be expected if the s[p- carbon of the radical were rapidly rotating or inverting with respect to the remainder of the molecule ... 

The preferred stereochemistry of addition to cyclic alkenes is anti The additions are not as highly stereoselective as hydrogen bromide addition, however. 

Grignard reagents that contain a /3-hydrogen—e.g. 15—can reduce a carbonyl substrate by transfer of that hydrogen as a side-reaction. The so-called Grignard reduction is likely to proceed via a six-membered cyclic transition state 16 the alkyl group of alkylmagnesium compound 15 is thereby converted into an alkene 17. 

In the next step, one of the borane-hydrogens is transferred to a sp -carbon center of the alkene and a carbon-boron bond is formed, via a four-membered cyclic transition state 6. A mono-alkyIborane R-BH2 molecule thus formed can react the same way with two other alkene molecules, to yield a trialkylborane R3B. In case of tri- and tctra-substituted alkenes—e.g. 2-methylbut-2-ene 7 and 2,3-dimethylbut-2-ene 9—which lead to sterically demanding alkyl-substituents at the boron center, borane will react with only two or even only one equivalent of alkene, to yield a alkylborane or mono alky Iborane respectively ... 

Alkenes with at least one vinjdic hydrogen undergo oxidative cleavage when treated with ozone, yielding aldehydes (Section 7.9). If the ozonolysis reaction is carried out on a cyclic alkene, a dicarbonyl compound results. 

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