Intermolecular Hydrophosphination of Alkynes and Related Carbon−Carbon Multiple Bonds Catalyzed by Organoytterbiums
- 23 July 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 68 (17) , 6554-6565
- https://doi.org/10.1021/jo030163g
Abstract
Intermolecular hydrophosphination of alkynes with diphenylphosphine is catalyzed by a Yb−imine complex, [Yb(η2-Ph2CNPh)(hmpa)3], to give alkenylphosphines and phosphine oxides after oxidative workup in good yields under mild conditions. This reaction is also applicable to various carbon−carbon multiple bonds such as conjugated diynes and dienes, allenes, and styrene derivatives. Regio- and stereoselectivity and the scope and limitation of the present reaction clearly differ from those of the corresponding radical reaction. Instead, the reaction takes place through insertion of alkynes to a Yb−PPh2 species, followed by protonation. In fact, the Yb−phosphido complex, [Yb(PPh2)2(hmpa)3], is obtained from the imine complex and phosphine, which exhibits similar catalyst activity for the hydrophosphination. The empirical rate law is ν = k[catalyst]2 [alkyne]1[phosphine]0 at least under the standard conditions.Keywords
This publication has 17 references indexed in Scilit:
- “Widening the Roof”: Synthesis and Characterization of New ChiralC1-Symmetric Octahydrofluorenyl Organolanthanide Catalysts and Their Implementation in the Stereoselective Cyclizations of Aminoalkenes and PhosphinoalkenesOrganometallics, 2001
- Reactivity of lithium diphenylphosphonium diylides towards phosphorus electrophiles: Synthesis of α,β-unsaturated phosphorus compoundsJournal of Organometallic Chemistry, 2001
- Organolanthanide-Catalyzed Intramolecular Hydrophosphination/Cyclization of Phosphinoalkenes and PhosphinoalkynesJournal of the American Chemical Society, 2000
- Dehydrogenative Silylation of Amines and Hydrosilylation of Imines Catalyzed by Ytterbium−Imine ComplexesThe Journal of Organic Chemistry, 1999
- Platinum-Catalyzed Acrylonitrile Hydrophosphination via Olefin Insertion into a Pt−P BondJournal of the American Chemical Society, 1997
- The First Isolation and Structural Characterization of a Lanthanoid−Imine Azametallacyclopropane Complex, [Yb(η2-Ph2CNPh)(hmpa)3]Organometallics, 1996
- Preparation of vinylphosphines by means of free radical addition of diphenylphosphine to alkynes and allenesJournal of Organometallic Chemistry, 1991
- Organolanthanide-centered hydroamination/cyclization of aminoolefins. Expedient oxidative access to catalytic cyclesOrganometallics, 1990
- Metallorganische verbindungen der lanthanoideJournal of Organometallic Chemistry, 1990
- Enantioselektive Katalyse: VII. Komplexe von (P(R,S),3R,4R,P′(R,S))-3,4-Bis(phenylphosphino)pyrrolidinen. Die Darstellung optisch reiner 1,2-Bisphosphanliganden mit vier Stereozentren, die zusätzliche funktionnelle Gruppen enthaltenJournal of Organometallic Chemistry, 1989