Synthesis of new 3-(dialkoxyphosphoryl)butenoates and their enantioselective hydrogenation

Citation
R. Kadyrov et al., Synthesis of new 3-(dialkoxyphosphoryl)butenoates and their enantioselective hydrogenation, SYNTHESIS-S, (6), 1999, pp. 1056-1062
Citations number
42
Categorie Soggetti
Chemistry & Analysis","Organic Chemistry/Polymer Science
Journal title
SYNTHESIS-STUTTGART
ISSN journal
00397881 → ACNP
Issue
6
Year of publication
1999
Pages
1056 - 1062
Database
ISI
SICI code
0039-7881(199906):6<1056:SON3AT>2.0.ZU;2-B
Abstract
(E)-3-Dialkoxyphosphorylbut-2-enoates, readily available by the dehydration of the 3-dialkoxyphosphoryl-3-hydroxybutyrates are converted to 3-dialkoxy phosphorylbut-3-enoates by Pd(II)-catalyzed photochemically assisted double bond migration. Hydrogenation of the latter catalyzed by chiral rhodium co mplexes affords 3-dialkoxyphosphorylbutyrates with higher rates and enantio selectivity (98% ee) than the hydrogenation of the (E)-3-dialkoxyphosphoryl but-2-enoates. The low activity of the rhodium complexes with bisphosphinit e ligands is caused by low affinity for complexation of the unsaturated pho sphonate.