Modular Catalysts for Diene Cycloisomerization: Rapid and Enantioselective Variants for Bicyclopropane Synthesis
- 15 September 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 128 (40) , 13290-13297
- https://doi.org/10.1021/ja064335d
Abstract
Deconstructing the tridentate (triphos)Pt(II) first-generation catalysts into mixed diphosphine/monophosphine combinations (P2P) has led to new, more active catalysts for the cycloisomerization of 1,6-, and 1,7-dienes into bicyclo-[3.1.0] and -[4.1.0] products. When the diphosphine was the small bite angle dppm, reaction rates were ∼20-fold faster than with triphos, although reaction rates and diastereoselectivities were also sensitive to the monophosphine (PMe3 being optimal for rate, PPh3 being optimal for selectivity). When the diphosphine was xyl-BINAP or SEGPHOS, the catalysts were enantioselective, and enantio-ratios up to 98:2 were observed. Both sets of catalysts showed enhanced functional group tolerance in comparison to the original (triphos)Pt2+ catalyst. X-ray structures for both precatalysts are also reported.Keywords
This publication has 24 references indexed in Scilit:
- Catalytic Enantioselective Conia-Ene ReactionJournal of the American Chemical Society, 2005
- Rhodium-Catalyzed Cycloisomerization of 1,6-Enynes with an Intramolecular Halogen Shift: Reaction Scope and MechanismJournal of the American Chemical Society, 2004
- Using Ligand Bite Angles To Control the Hydricity of Palladium Diphosphine ComplexesJournal of the American Chemical Society, 2004
- Coordination of Alkenes at a Highly Electrophilic Site. New Dicationic Platinum(II) Complexes: Synthesis, Structure, and Reactions with NucleophilesOrganometallics, 2002
- Ligand Bite Angle Effects in Metal-catalyzed C−C Bond FormationChemical Reviews, 2000
- Conformational dependence of the circular dichroism of N-nitrosopyrrolidinesJournal of the American Chemical Society, 1993
- Restricted gearing and residual stereoisomerism in bis(1,4-dimethyl-9-triptycyl)methaneJournal of the American Chemical Society, 1981
- Periodate oxidation of vicinal hydroxyls. Applications to student experimentsJournal of Chemical Education, 1977
- Stereospecific cyclopropane-ring formation by 1,3-deoxymetalation of trimethyltin-substituted norbornyl mesylatesJournal of the American Chemical Society, 1974
- Study of the interfacial properties of water by gas chromatographyAccounts of Chemical Research, 1973