Journal of the American Chemical Society 2004-08-25

Alkylation of alkenes: ethylaluminum sesquichloride-mediated hydro-alkyl additions with alkyl chloroformates and di-tert-butylpyrocarbonate.

Ursula Biermann, Jürgen O Metzger

Index: J. Am. Chem. Soc. 126(33) , 10319-30, (2004)

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Abstract

A general method for the hydro-alkyl addition to the nonactivated C=C double bond of alkenes using alkyl chloroformates (primary, secondary), 12, and di-tert-butylpyrocarbonate, 52, mediated by ethylaluminum sesquichloride (Et(3)Al(2)Cl(3)) has been developed. Reaction of 12 and 52, respectively, with Et(3)Al(2)Cl(3) gives an alkyl cation which is added to the alkene; hydride transfer to the adduct carbenium ion or, if applicable, 1,2-H shift followed by hydride transfer from Et(3)Al(2)Cl(3) to the rearranged adduct carbenium ion gives the saturated addition product. The reaction has been applied to 1-alkenes, 2-methyl-1-alkenes, internal double bonds, and to three cyclic alkenes. Special interest has been focused on alkylations of unsaturated fatty compounds, such as oleic acid (2), which are important renewable feedstocks. 2-Methylalkanes, 3-methylalkanes, 2,4-dimethylalkanes, 2,3-dimethylalkanes, 2,2,4-trimethylalkanes, cyclohexylalkanes, and carboxylic acids and esters with the respective branched alkyl chain have been synthesized with good to moderate yields.