Carbocations, from epoxides

Other electrophiles include acylium ions produced from acid chlorides, carbocations from tertiary halides or secondary benzylic halides, activated enones, and epoxides all in the presence of Lewis acid. In each case the new bond is highlighted in black. 

Allyl silanes are rather like silyl enol ethers they react with electrophiles, provided they are activated, for example by a Lewis acid. Titanium tetrachloride is widely used but other successful Lewis acids include boron trifluoride, aluminium chloride, and trimethylsilyl triflate. Electrophiles include acylium ions produced from acid chlorides, carbocations from tertiary halides or secondary benzylic halides, activated enones, and epoxides all in the presence of Lewis acid. In each case the new bond is highlighted in black. 

Strong acids produce carbocations from a variety of functional molecules. Protonation of alcohols, epoxides, carbonyl compounds, and alkenes does so. Lewis acids such as anhydrous aluminum chloride can combine with these substrates and can also remove halide ions from carbon to give carbocations. Diazotization of primary amines in acid solution is another source. 

The example in Equation 7.17 shows the formation of a carbocation from an epoxide, reaction with an alkene, and finally aromatic substitution onafuran [32]. 

Hydride Transfer In some reactions, a hydride ion is transferred to or from the substrate. The reduction of epoxides with LiAlH4 is an example (10-85). Another is the Cannizzaro reaction (19-60). Reactions in which a carbocation abstracts a hydride ion belong in this category ... 

The formation of the primary carbocation can be achieved by treatment of an alkene or an epoxide with a Bronsted or a Lewis add, by elimination of water from an alcohol or an alcohol from an acetal and by readion of enones and imines with Lewis acids. The two latter reactions may also be classified under anionic domino reactions depending on the following steps. 

Energies for various possible arenium ions and regioisomeric benzylic cations were computed at the DFT B3LYP/6-31G(d) level or by AMI for comparison with the experimental results. These findings provided further evidence in support of the stability sequence 1-pyrenyl > 4-pyrenyl > 2-pyrenyl in a-pyrene-substituted carbocations as models for the intermediates arising from BaP-epoxide ring opening (Fig. 10). 

A parallel was drawn between stable ion and AMI studies of methylphenanthrenes and solvolytic studies of K-region and non-K-region phenanthrene oxides. The carbocation formed by opening of the 1,2-epoxide closely resembled the 2-methylphenanthrene cation (and 7H ), and the regiochemistry of phenol formation (1-phenanthrol) could be understood. Similarly, phenanthrenium cations derived from the 3-methyl and dimethylated compounds served as models for carbo-cations formed by solvolysis of phenanthrene-3,4-epoxide (formation of 4-phenanthrol following hydride shift). 

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