Alkylation of α-Halo Diketones via Enol Phosphate Intermediate

Chemistry Letters

Volumn 32, Issue 11, 2003, Pages 994-995

  Onishi, Jim Yoshitaka ^a,b   Takuwa, Tomofumi ^a,b   Mukaiyama, Teruaki ^a,b  

^a KITASATO INSTITUTE   (Japan)

^b KITASATO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CARBONYL DERIVATIVE; COPPER DERIVATIVE; DIKETONE; KETONE DERIVATIVE; PHOSPHATE; PHOSPHORUS DERIVATIVE; TRIETHYL PHOSPHITE; UNCLASSIFIED DRUG;

ADDITION REACTION; ALKYLATION; ARTICLE; CHEMICAL STRUCTURE; QUANTUM YIELD;

EID: 0842263695     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.2003.994     Document Type: Article

References (23)

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18. 2, tautomerization occurred at room temperature and a 1:1 mixture of cis and trans isomers was observed within 1 h.
19. A small amount of alkylation product (8% yield) was isolated from the organocuprate addition of cis enol phosphate in THF at -78°C for 2 h, presumably due to tautomerization to the trans isomer. Alkylation of trans enol phosphate formed the desired product along with reduced 1,3-diketone (56% and 23% yields, respectively) under similar conditions. No increase in yield was observed with extended reaction time or higher temperatures (-50 and -30°C).
20. 1H NMR analysis using an internal standard.
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22. For bromination of 1,3-dicarbonyl compounds see; D. W. Gillon, I. J. Forrest, G. D. Meakins, M. D. Tirel, and J. D. Wallis, J. Chem. Soc., Perkin Trans. 1, 1983, 341; S.-F. Cheng, C.-S. Lin, and L. K. Liu, J. Chin. Chem. Soc., 44, 309 (1997).
23. It was also noted that 1,3-dicarbonyl compound (0.22 mmol) can be brominated with NBS (0.23 mmol) at room temperature within 30 min in THF (10 mL) and then addition of triethyl phosphite (0.25 mmol) at 0°C formed the enol phosphate intermediate in situ within 1 h. Subsequent addition of the higher-order organocuprate (0.56 mmol) in the presence of boron trifluoride diethyl etherate (0.56 mmol) via canula at -78°C in THF (10 mL) and stirring for 2 h formed the β-substituted α,β-unsaturated ketone in high yield in a one-pot procedure.