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Volumn 47, Issue 7, 2008, Pages 1312-1316

Highly regio-, diastereo-, and enantioselective [2+2+2] cycloaddition of 1,6-enynes with electron-deficient ketones catalyzed by a cationic Rh I/H8-binap complex

Author keywords

Asymmetric catalysis; Cycloaddition; Enynes; Ketones; Rhodium

Indexed keywords

AMIDES; ENANTIOSELECTIVITY; KETONES; RHODIUM;

EID: 53549104121     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200704758     Document Type: Article
Times cited : (90)

References (62)
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    • We investigated the chemoselectivity of the present cycloaddition with respect to the reactivity of a carbonyl group in the presence of an alkyne moiety and found that the carbonyl group of an alkynyl ketoester reacted with a 1,6-enyne, although the cycloadduct could not be isolated in pure form. For the [2+2+2] cycloaddition of 1,6-enynes with monoalkynes under the catalysis of cationic complexes of RhI with modified binap ligands, see: a P. A. Evans, K. W. Lai, J. R. Sawyer, J. Am. Chem. Soc. 2005, 127, 12466;
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    • When the ligand (R)-binap was used, the cycloaddition products were obtained in higher yields than with (R)-H8-binap.
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    • CCDC-662606 (3ab) and CCDC-662607 (6eh) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
    • CCDC-662606 (3ab) and CCDC-662607 (6eh) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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    • I/(R)-binap catalyst was reported. However, the use of (R)-binap required the very slow addition (over a period of 30 min) of the enyne substrate; furthermore, neither the absolute configuration of the product nor electronic effects on the reaction were determined: K. Tsuchikama, Y. Kuwata, Y. Tahara, Y. Yoshinami, T. Shibata, Org. Lett. 2007, 9, 3097.
    • I/(R)-binap catalyst was reported. However, the use of (R)-binap required the very slow addition (over a period of 30 min) of the enyne substrate; furthermore, neither the absolute configuration of the product nor electronic effects on the reaction were determined: K. Tsuchikama, Y. Kuwata, Y. Tahara, Y. Yoshinami, T. Shibata, Org. Lett. 2007, 9, 3097.


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