81455-05-2Relevant academic research and scientific papers
The Chemistry of Pentavalent Organobismuth Reagents. Part 8. Phenylation and Oxidation of Alcohols by Tetraphenylbismuth Esters
Barton, Derek H. R.,Finet, Jean-Pierre,Motherwell, William B.,Pichon, Clotilde
, p. 251 - 260 (2007/10/02)
Tetraphenylbismuth trifluoroacetate under neutral or slightly acidic conditions O-phenylates primary alcohols in reasonable (65-75percent) yield, but gives only moderate yields with secondary alcohols and no O-phenylation with tertiary alcohols.An SN2 type mechanism is proposed with attack of oxygen on aryl carbon.In contrast, the reaction of Bi(V) reagents with alcohols under basic conditions gives, exclusively, oxidation, often with benzene as a leaving group.The presence of a Bi(V) intermediate with a bismuth-oxygen bond has been proved in several different ways using n.m.r. spectroscopy.Thus the reactions of alcohols with Bi(V) reagents parallel the corresponding reactions with phenols.
Conversion of One Hydroxy Group in a Diol to a Phenyl Ether with Triphenylbismuth Diacetate, a New Glycol Reaction Showing Strong Axial Preference in Six-Membered Rings
David, Serge,Thieffry, Annie
, p. 441 - 447 (2007/10/02)
After being refluxed for a few hours, a dichloromethane solution of a diol with triphenylbismuth diacetate gave in most cases excellent yields of a monophenyl ether.No diphenylated products were found.Tertiary hydroxy groups were only phenylated in bis tertiary diols, and then in poor yield.Increasing the distance between the hydroxy groups up to six carbon atoms decreased the speed of the reaction which nevertheless was still preparatively useful.Diols in flexible rings behaved like their acyclic counterparts.The course of the reaction was also examined with someconformationally rigid molecules: trans-4-tert-butyl-cis-2-hydroxycyclohexanol, trans-4-tert-butyl-trans-2-hydroxycyclohexanol, cholestane-2α,3α-diol, cholestane-2α,3β-diol, and pyranoside derivatives with the α-D-gluco, α-D-manno, α-D-galacto, and α-D-allo configurations.The phenylations of cis-diols were strongly regioselective for axial epimers, while those of trans, bis equatorial diols were undiscriminate and often much slower.A feasible general mechanism is proposed to explain these results.
SELECTIVE PHENYLATION IN MILD CONDITIONS OF ONE HYDROXY GROUP IN GLYCOLS WITH TRIPHENYLBISMUTH DIACETATE: A NEW SPECIFIC GLYCOL REACTION.
David, Serge,Thieffry, Annie
, p. 5063 - 5066 (2007/10/02)
Refluxing for 4-5 h a dichloromethane solution of diol in the presence of an equimolecular quantity of triphenylbismuth diacetate gave the monophenyl ether in good to excellent yield.
