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Volumn 11, Issue 13, 2005, Pages 3872-3880

Rhodium-catalyzed asymmetric aqueous Pauson-Khand-type reaction

Author keywords

Asymmetric catalysis; Cyclization; Pauson Khaiod reactions; Phosphane ligands; Rhodium

Indexed keywords

ADDITION REACTIONS; CATALYSTS; COLUMN CHROMATOGRAPHY; ELECTRONIC PROPERTIES; FREE ENERGY; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; RHODIUM; STEREOCHEMISTRY;

EID: 21244472680     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200401237     Document Type: Article
Times cited : (70)

References (93)
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    • ref. [14c]. For the most recent reference with molecular sieves as a CO gas reservoir, sec
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    • 6-mediated aqueous PKR, which uses water as a cosolvent and/or with the addition of surfactant (sodium dodecylsulfate (SDS)), see: a) M. E. Kraff, J. A. Wright, L. V. R. Boñaga, Tetrahedron Lett. 2003, 44, 3417;
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    • note
    • Air-stable ligand, enynes, and aldehyde were weighed on the bench top under air without special precautions.
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  • 61
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    • note
    • BINAP = 2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl. tol-BINAP = 2,2′-bis(di-p-tolylphosphanyl)-1,1′-binaphthyl, (R-R)-Et-DUPHOS = (-)-1,2-bis((2R,5R)-2,5-diethylphospholano)benzcnc; (S)-PHANEPHOS - (S)-(+)-4,12-bis(diphenylphosphano)-[2.2]-paracyclophane ; (S,S)-Et-FerroTANE = (-)-1,1′-bis((2S,4S)-2,4-diethy!phospholano)- ferrocene.
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    • note
    • 59% yield, 81% ee (under the same reaction conditions as in Table 1 except for the aldehyde loading).
  • 72
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    • For evidences for the role of dπ-pπ bonding in the rhodium-mediated reaction, see: a) K. Burgess, W. A. van der Donk, M. B. Jarstfer, M. J. Ohlmeyer, J. Am. Chem. Soc. 1991, 113, 6139. For models that assume that the complexation of the alkene/alkyne (π interaction) to the metal center is the rate stereochemical-determining step of the reaction, see:
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    • note
    • We thank a referee during the manuscript-reviewing process for the suggestion of other factors that could be responsible for the observed electronic influence, for example, the interaction of the phenyl π system with the Rh center, which differs in strength and geometry depending on the substitutent (electron-donating group or electron-withdrawing group), or an electronically induced shift from an early to a late transition state.


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