title: Rapid Asymmetric Transfer Hydroformylation (ATHF) of Disubstituted Alkenes Using Paraformaldehyde as a Syngas Surrogate.
abstract: As an alternative to conventional asymmetric hydroformylation (AHF), asymmetric transfer hydroformylation (ATHF) by using formaldehyde as a surrogate for syngas is reported. A catalyst derived from commercially available [Rh(acac)(CO)2 ] (acac=acetylacetonate) and 1,2-bis[(2S,5S)-2,5-diphenylphospholano]ethane(1,5-cyclooctadiene) (Ph-BPE) stands out in terms of both activity and enantioselectivity. Remarkably, not only are high selectivities achievable, the reactions are very simple to perform, and higher enantioselectivity (up to 96 % ee) and/or turnover frequencies than those achievable by using the same catalyst (or other leading catalysts) can be obtained by using typical conditions for AHF.
authors.affiliation: School of Chemistry, University of St Andrews, EaStCHEM, St Andrews, Fife, KY16 9ST (UK), Fax: (+44)1334-463808.
authors.forename: José A
authors.initials: JA
authors.lastname: Fuentes
authors.affiliation: School of Chemistry, University of St Andrews, EaStCHEM, St Andrews, Fife, KY16 9ST (UK), Fax: (+44)1334-463808.
authors.forename: Rachael
authors.initials: R
authors.lastname: Pittaway
authors.affiliation: School of Chemistry, University of St Andrews, EaStCHEM, St Andrews, Fife, KY16 9ST (UK), Fax: (+44)1334-463808. mc28@st-andrews.ac.uk.
authors.forename: Matthew L
authors.initials: ML
authors.lastname: Clarke
keywords: carbonylation; enantioselectivity; formaldehyde; hydroformylation; microwave chemistry