A convenient and asymmetric protocol for the synthesis of natural products containing chiral alkyl Chains via Zr-catalyzed asymmetric carboalumination of alkenes. Synthesis of phytol and vitamins E and K

Organic Letters

Volumn 3, Issue 21, 2001, Pages 3253-3256

  Huo, Shouquan ^a   Negishi, Ei Ichi ^a  

^a PURDUE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; ALPHA TOCOPHEROL; ALUMINUM; BIOLOGICAL PRODUCT; ORGANOMETALLIC COMPOUND; PHYTOL; VITAMIN K GROUP; ZIRCONIUM;

ALKYLATION; ARTICLE; CATALYSIS; CHEMISTRY; STEREOISOMERISM; SYNTHESIS;

ALKENES; ALKYLATION; ALUMINUM; BIOLOGICAL PRODUCTS; CATALYSIS; ORGANOMETALLIC COMPOUNDS; PHYTOL; STEREOISOMERISM; VITAMIN E; VITAMIN K; ZIRCONIUM;

EID: 0035909643     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol010142d     Document Type: Article

References (46)

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3. 2O accelerates the Zr-catalyzed methylalumination is notheworthy: Wipf, P.; Ribe, S. Org. Lett. 2000, 2, 1713. See also: Wipf, P.; Ribe, S. Org. Lett. 2001, 3, 1503.
4. 2O accelerates the Zr-catalyzed methylalumination is notheworthy: Wipf, P.; Ribe, S. Org. Lett. 2000, 2, 1713. See also: Wipf, P.; Ribe, S. Org. Lett. 2001, 3, 1503.
5. For Zr-catalyzed asymmetric carbomagnesation of allylically hetero-substituted alkenes, which evidently proceeds via cyclic carbozirconation and is therefore discrete from the reaction discussed herein, see: (a) Morken, J. P.; Didiuk, M. T.; Hoveyda, A. H. J. Am. Chem. Soc. 1993, 115, 6697.
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21. Although the origin of this significant difference is not clear, the possibility that Et and higher alkyls might exert a secondary chiral induction stemming from α-agostic interaction, which is uniquely absent in the case of Me, is an attractive notion to be pursued. For a recent discussion of the effect of α-agostic interaction in alkene polymerization, see: Grubbs, R. H.; Coates, G. W. Acc. Chem. Res. 1996, 29, 85. equation presented
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32. 3S).
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34. 2 = 0.7569R,R + 0.0169S,S + 0.1131R,S + 0.1131S,R. The statistically predicted overall % ee of 5 = ((0.7569-0.0169)/(0.7569 + 0.0169)) x 100 = 95.6%. The diastereomeric ratio of 5 = (0.7569 + 0.0169)/(2 x 0.1131) = 3.42.
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