Symmetrical alkene

When zirconocene alkene complexes are formed in the presence of an excess of the same alkene, symmetric dimers 30 are formed with high regio-and stereocontrol. Cross-coupling of different alkenes is not generally successful because the rate of alkene exchange from the first formed iq -alkene... 

The intermolecular McMurry reaction is first of all a suitable method for the synthesis of symmetrical alkenes. With a mixture of carbonyl compounds as starting material, the yield is often poor. An exception to this being the coupling of diaryl ketones with other carbonyl compounds, where the mixed coupling product can be obtained in good yield. For example benzophenone and acetone (stoichiometric ratio 1 4) are coupled in 94% yield. ... 

Methyl-2-hexcne has a disubstituted double bond, RCH=CHR, and would probably give a mixture of two alcohols with either hydration method since Markovnikov s rule does not apply to symmetrically substituted alkenes. 3-MethyI-3-hexene, however, has a trisubstituted double bond, and would give only the desired product on non-Markovnikov hydration using the hydroboration/oxidation method. 

Diethyl ether and other simple symmetrical ethers are prepared industrially by the sulfuric acid-catalyzed dehydration of alcohols. The reaction occurs by SN2 displacement of water from a protonated ethanol molecule by the oxygen atom of a second ethanol. Unfortunately, the method is limited to use with primary alcohols because secondary and tertiary alcohols dehydrate by an El mechanism to yield alkenes (Section 17.6). 

Inverse electron-demand Diels-Alder reaction of (E)-2-oxo-l-phenylsulfo-nyl-3-alkenes 81 with enolethers, catalyzed by a chiral titanium-based catalyst, afforded substituted dihydro pyranes (Equation 3.27) in excellent yields and with moderate to high levels of enantioselection [81]. The enantioselectivity is dependent on the bulkiness of the Ri group of the dienophile, and the best result was obtained when Ri was an isopropyl group. Better reaction yields and enantioselectivity [82, 83] were attained in the synthesis of substituted chiral pyranes by cycloaddition of heterodienes 82 with cyclic and acyclic enolethers, catalyzed by C2-symmetric chiral Cu(II) complexes 83 (Scheme 3.16). 

Alkylboranes can be coupled by treatment with silver nitrate and base." Since alkylboranes are easily prepared from alkenes (15-16), this is essentially a way of coupling and reducing alkenes in fact, alkenes can be hydroborated and coupled in the same flask. For symmetrical coupling (R = R ) yields range from 60 to 80% for terminal alkenes and from 35 to 50% for internal ones. Unsymmetrical coupling has also been carried out, but with lower yields. Arylboranes react similarly, yielding biaryls. The mechanism is probably of the free-radical type. 

For carbenes or carbenoids of the type R—C—R there is another aspect of stereochemistry. When these species are added to all but symmetrical alkenes, two isomers are possible, even if the four groups originally on the double-bond carbons maintain their configurations ... 

Sp and sp-carbon atoms such as a carbonyl group and an alkene are reactive cent-ersl in many kinds of reactions. The n orbitals of a simple molecule such as ethylene or formaldehyde are symmetric in magnimde and antisymmetric in sign with respect to reflection in the molecular plane. Various attempts have been made to rationalize stereoselectivities, and several general ideas have emerged, including a steric basis and an orbital basis. 

Dicarbonyl disconnection of symmetrical (38) again reveals a suitable 1,6-dicarbonyl starting material (39) but reconnection gives an impossibly strained alkene (40). 

Epoxides are ol course as easy to make from un-symmetrical, e.g. (29) as from symmetrical, e.g. (26), alkenes. The more stable carbonlum ion is again formed. Hydride shift is preferred to alkyl shift except in the favourable 6 5 ring contraction. 

Similarly, when adding two different groups across a symmetrical alkene, regiochemistry is also irrelevant ... 

All of the examples above were symmetrical alkenes, so regiochemistry was not relevant. Now let s consider a case where regiochemistry is relevant. With an un-symmetrical alkene, we must decide where to put the H and where to put the X. For... 

Attempts have been made to exploit the intrinsic C2 symmetry of the phenolate-based dinickel core in enantioselective catalytic reactions. Therefore, enantiomerically pure C2-symmetric ligands such as (736a) and the corresponding dinickel systems (736b) have been prepared ( Equation (27)),1890 and (736b) was tested in the epoxidation of unfunctionalized alkenes with sodium hypochlorite as the oxidant. The catalytic reaction was found to be highly pH dependent with an optimum at a pH of 9. While the complex is catalytically active, significant enantioselectivity was not achieved. 

A combination of a metathesis and a Diels-Alder reaction was published by North and coworkers [263]. However, this is not a true domino reaction, as the dienophile (e. g., maleic anhydride) was added after the in situ formation of the his-butadiene 6/3-89 from the fois-alkyne 6/3-88 and ethylene. The final product is the fois-cycloadduct 6/3-90, which was obtained in 34% yield. Using styrene as an un-symmetrical alkene instead of ethylene, the mono-cycloadduct 6/3-91 was formed as a mixture of double-bond isomers, in 38% yield (Scheme 6/3.26). 

Saito and coworkers have used C2-symmetrical alkenes derived from a variety of tartaric acid derivatives, for controller in discriminating 71 faces of dipolarophile in nitrone cycloaddition. Excellent endolexo and diastereofacial selectivity (de) are obtained. Endo transition state assembly shown in Eq. 8.50 could be responsible for the formation of preferred distereoisom-... 

Microwave-assisted Heck reactions have also been carried out with triflates as coupling partners, involving some very complex molecules. Winterfeld and coworkers have reported a multigram synthesis of a complex non-symmetrical bis-steroidal diene by microwave-promoted coupling of the corresponding alkene and triflate steroidal moieties (Scheme 6.8) [27]. 

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