Synthesis of Short-Chain Alkenyl Ethers from Primary and Bio-sourced Alcohols via the Nickel-Catalyzed Hydroalkoxylation Reaction of Butadiene and Derivatives
Hydroalkoxylation of butadiene has been performed in the presence of nickel precatalysts associated with chelating diphosphine ligands. High butadiene conversions and selectivities forming alkyl butenyl ethers were obtained with low catalyst loading. Reactions were performed with a wide scope of primary alcohols including benzylic alcohol derivatives and bio-sourced alcohols. In the same way, the scope of dienes that can be reacted according to this reaction has been also studied. Substituted butadiene derivatives have shown a lower reactivity compared to butadiene. Isoprene formed OC5 alkenyl ethers with a high regioselectivity for one branched isomeric form.
Chemo- and regioselective reductive transposition of allylic alcohol derivatives via iridium or rhodium catalysis
We report highly chemo- and regioselective reductive transpositions of methyl carbonates to furnish olefin products with complementary regioselectivity to that of established Pd-catalysis. These Rh- and Ir-catalysed transformations proceed under mild conditions and enable selective deoxygenation in the presence of functional groups that are susceptible to reduction by metal hydrides.
Lundgren, Rylan J.,Thomas, Bryce N.
supporting information
p. 958 - 961
(2016/01/20)
Nickel-catalysed hydroalkoxylation reaction of 1,3-butadiene: Ligand controlled selectivity for the efficient and atom-economical synthesis of alkylbutenyl ethers
The nickel-catalysed hydroalkoxylation of butadiene is promoted by a nickel(0)/dppb catalyst (dppb=1,4-bis(diphenylphosphino)butane; see scheme). By following this new synthetic procedure, alkylbutenyl ethers are readily obtained from an alcohol and 1,3-butadiene with exclusion of dimerisation and telomerisation products. Copyright