The kinetic resolution of allylic alcohols by a non-enzymatic acylation catalyst; application to natural product synthesis

Chemical Communications

Volumn , Issue 12, 2000, Pages 1009-1010

  Bellemin Laponnaz, Stéphane ^a   Tweddell, Jennifer ^a   Ruble, J Craig ^a   Breitling, Frank M ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL ALCOHOL; BACLOFEN; EPOTHILONE A; NATURAL PRODUCT;

ACYLATION; ARTICLE; CATALYST; CHIRALITY; DRUG SYNTHESIS; ENANTIOMER;

EID: 0034697763     PISSN: 13597345     EISSN: None     Source Type: Journal    
DOI: 10.1039/b002041i     Document Type: Article

References (27)

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3. Selectivity factor = [(rate of fast-reacting enantiomer)/(rate of slow-reacting enantiomer)]. For a review of kinetic resolution, see: H. B. Kagan and J. C. Fiaud, Top. Stereochem., 1988, 18, 249.
4. For a review of enantioselective acylations of alcohols by enzymes, see: K. Drauz and H. Waldmann, Enzyme Catalysis in Organic Synthesis: A Comprehensive Handbook, VCH, New York, 1995.
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17. Fourteen examples with s > 10: refs. 5, 6 and 9(a)-(c).
18. Thirteen examples with s > 10: refs. 6-8.
19. Eight examples with s > 10: ref. 9(d).
20. Three examples with s > 10: refs. 5(b) and 9(a).
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26. For commentaries, see: P. G. Schultz, Proc. Natl. Acad. Sci. USA, 1998, 95, 14 590; S. Borman, Chem. Eng. News, Dec. 14, 1998, p. 15.
27. 3-EtOAc) to separate the alcohol and the acetate from the catalyst [27.6 mg (95%) of pure catalyst was recovered]. The alcohol and the acetate were then separated by flash chromatography (10 → 25% EtOAc-hexanes), which afforded 0.70 g (52%) of acetate (HPLC analysis ⇒ 91.8% ee) and 0.55 g (47%) of alcohol (HPLC analysis ⇒ 98.0% ee). These ee values correspond to a selectivity factor (s) of 107 at 51.6% conversion.