Alkyl-branched Fatty Compounds: Hydro-alkylation of Non-activated Alkenes with Haloalkanes Mediated by Ethylaluminum Sesquichloride†

The general method for the cationic hydro-alkyl addition to the nonactivated C=C double bond of alkenes mediated by ethylaluminum sesquichloride (Et3Al2Cl3) has been importantly improved and simplified by using haloalkanes (primary, secondary, tertiary) instead of alkyl chloroformates as alkylating agent and performing the reaction without any additional solvent. The protocol is especially suited to perform the hydro-alkylation of internal double bonds. Reaction of the haloalkane with Et3Al2Cl3 gives an alkyl cation which is added to the alkene; hydride transfer from Et3Al2Cl3 to the adduct carbenium ion gives the saturated addition product. Primary halo alkanes give the same addition product as the respective secondary halo alkane because of 1,2-H shift yielding the secondary carbenium ions. In the case of 1-alkenes triethylsilane has to be used as additional hydride donor to avoid di-and oligomerization. Special interest has been focused on alkylation of unsaturated fatty compounds, which are important renewable feedstocks, mostly (Z)-configured such as methyl oleate, high oleic sunflower oil, neopentyl glycol dioleate, but also (E)configured, that is, dimethyl (E)-icos-10-enedioate, and with terminal double bond such as methyl 10-undecenoate. The respective alkyl branched fatty compounds were obtained after simple work-up with excellent to good yields. The protocol was scaled up without problems to > 0.5 mol.