Chemoenzymatic synthesis of a mixed phosphine-phosphine oxide catalyst and its application to asymmetric allylation of aldehydes and hydrogenation of alkenes.
The chemoenzymatic synthesis of a Lewis basic phosphine-phosphine oxide organocatalyst from a cis-dihydrodiol metabolite of bromobenzene proceeds via a palladium-catalysed carbon-phosphorus bond coupling and a novel room temperature Arbuzov [2,3]-sigmatropic rearrangement of an allylic diphenylphosphinite. Allylation of aromatic aldehydes were catalysed by the Lewis basic organocatalyst giving homoallylic alcohols in up to 57% ee. This compound also functioned as a ligand for rhodium-catalysed asymmetric hydrogenation of acetamidoacrylate giving reduction products with ee values of up to 84%.
School of Chemistry and Chemical Engineering, Queen's University, Belfast, BT9 5AG, UK. dr.boyd@qub.ac.uk
Derek R
DR
Boyd
Mark
M
Bell
Katherine S
KS
Dunne
Brian
B
Kelly
Paul J
PJ
Stevenson
John F
JF
Malone
Christopher C R
CC
Allen
D000447:Aldehydes / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D006865:Hydrogenation; D058115:Lewis Bases / Q000737:chemistry; D008024:Ligands; D010720:Phosphines / Q000138:chemical synthesis*; D020005:Propanols / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry; D013237:Stereoisomerism
D000447:Aldehydes; D000475:Alkenes; D058115:Lewis Bases; D008024:Ligands; D010720:Phosphines; D020005:Propanols; C006463:allyl alcohol; D012238:Rhodium; C044646:phosphine