Direct Catalytic Asymmetric Aldol Additions of Methyl Ynones. Spontaneous Reversal in the Sense of Enantioinduction

Journal of the American Chemical Society

Volumn 126, Issue 9, 2004, Pages 2660-2661

  Trost, Barry M ^a   Fettes, Alec ^a   Shireman, Brock T ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBONYL DERIVATIVE; METHYL GROUP; METHYL YNONE DERIVATIVE; UNCLASSIFIED DRUG; ZINC;

ADDITION REACTION; ALDOL REACTION; ARTICLE; ASYMMETRIC SYNTHESIS; CATALYSIS; ENANTIOINDUCTION; MOLECULAR RECOGNITION; PROCESS DESIGN; PROCESS OPTIMIZATION; PRODUCTIVITY; REACTION ANALYSIS;

ALCOHOLS; ALDEHYDES; ALKYNES; CATALYSIS; KETONES; STEREOISOMERISM;

EID: 1542347976     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja038666r     Document Type: Article

References (20)

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3. For reviews, see: (c) Alcaide, B.; Almendros, P. Eur. J. Org. Chem. 2002, 1595-1601.
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5. Shibasaki reported a moderately diastereoselective direct aldol addition of an ynone in his recent fostriecin synthesis: Fujii, K.; Maki, K.; Kanai, M.; Shibasaki, M. Org. Lett. 2003, 5, 733-736.
6. Aldol reactions: (a) Trost, B.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003-12004.
7. (b) Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367-3368.
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9. (d) Trost, B.; Yeh, V. S. C. Org. Lett. 2002, 4, 3513-3516.
10. (e) Henry reactions: Trost, B. M.; Yeh, V. S. C. Angew. Chem., Int. Ed. 2002, 41, 861-863.
11. (f) Trost, B. M.; Yeh, V. S. C.; Ito, H.; Bremeyer, N. Org. Lett. 2002, 4, 2621-2623.
12. Mannich-type reactions: (g) Trost, B. M.; Terrell, L. R. J. Am. Chem. Soc. 2003, 125, 338-339.
13. Diol desymmetrization: (h) Trost, B. M.; Mino, T. J. Am. Chem. Soc. 2003, 125, 2410-2411.
14. The absolute configuration was assigned by converting aldol 6 into its O-methyl mandelate ester. For details, see: Trost, B. M.; Bunt, R. C.; Pulley, S. R. J. Org. Chem. 1994, 59, 4202-4205.
15. When rac-6 was submitted to the reaction conditions, the enantioselectivity increased to 24% after 3.5 h. It could also be shown that only ent-6 eliminates under the reaction conditions, while 6 is stable over extended periods of time (24 h).
16. ent-6 as additive had little effect on the reaction.
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