3875-51-2Relevant articles and documents
Alkylation of alkenes: Ethylaluminum sesquichloride-mediated hydro-alkyl additions with alkyl chloroformates and di-tert-butylpyrocarbonate
Biermann, Ursula,Metzger, Juergen O.
, p. 10319 - 10330 (2007/10/03)
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 (Et3Al2Cl3) has been developed. Reaction of 12 and 52, respectively, with Et3Al2Cl3 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 Et3Al2Cl3 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.
REACTIONS OF 1-HALO-5-HEXENES WITH ALKYLLITHIUMS. EVIDENCE FOR A PRONOUNCED HALOGEN EFFECT ON THE MECHANISM OF THE METAL-HALOGEN INTERCHANGE REACTION OF PRIMARY ALKYL HALIDES
Bailey, William F.,Patricia, Jeffrey J.,Nurmi, Timo T.
, p. 1865 - 1868 (2007/10/02)
Reaction of t-BuLi with 1-halo-5-hexenes and 1-halo-6-methyl-5-heptenes at -78 gradC has revealed that, whereas 1 deg alkyl iodides are cleanly converted to alkyllithiums in a non-radical process, the corresponding 1 deg alkyl bromides undergo interchange at least partially via a radical-mediated, SET pathway.
