An efficient route to chiral α- and β-hydroxyalkanephosphonates

Journal of Organic Chemistry

Volumn 68, Issue 12, 2003, Pages 4815-4818

  Pàmies, Oscar ^a   Bäckvall, Jan E ^a  

^a STOCKHOLM UNIVERSITY   (Sweden)

Author keywords

[No Author keywords available]

Indexed keywords

KINETIC RESOLUTION;

ALCOHOLS; ENZYME KINETICS; ISOMERIZATION; RUTHENIUM; STEREOCHEMISTRY;

PARAFFINS;

ACETIC ACID DERIVATIVE; ALCOHOL; PHOSPHONIC ACID DERIVATIVE; RUTHENIUM;

ARTICLE; CATALYSIS; CHIRALITY; ENANTIOMER; RACEMIC MIXTURE; REACTION ANALYSIS;

EID: 0037941143     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo026888m     Document Type: Article

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34. Other bases such as triethylamine, pyridine, and sodium methoxide also gave access to the desired α-hydroxyphosphonates, but either the reaction times were substantially longer or the reactions conditions were less convenient.
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36. The use of vinyl acetate, commonly used as acyl donor, results in the formation of acetaldehyde after the acyl-transfer process, which interferes with the ruthenium hydrogen-transfer catalysts usually employed in the DKR; see ref 10b.
37. The solubility of the Ru catalyst 4 in toluene is higher than in ethers and other solvents, and this results in higher racemization rates; see ref 11f.
38. The KR of 1d using CALB proceeded with low activity (<5% after 5 h).
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42. The presence of base can cause undesired side reactions in the substrate and/or product. Moreover, the basicity and quantity of base have to be carefully tuned to not affect the enzyme.
43. Similar results were obtained by adding only 1.2 equiv of acyl donor 3.
44. The Ru decomposition triggers, at the same time, the progressive deactivation of the enzyme. Similar behavior has been recently observed when DKR on ti 0-bromo alcohols was attempted; see: Pàmies, O.; Bäckvall, J.-E. J. Org. Chem. 2002, 67, 9006.
45. The addition of 6 also reduces the efficiency of the DKR. Thus, the corresponding acetate was obtained in only 53% yield (>99% ee) after 24 h. This is attributed to the competition between alcohols 6 and 1 in the transfer hydrogenation process.
46. The amount of ketone 5 increased when the amount of acyl donor added was lowered to 1.2 equiv.
47. For substrate 1b, the addition of HCl causes decomposition of the product. Therefore, it was purified by column chromatography using ethyl acetate as eluent and then by bulb-to-bulb distillation.
48. Alternatively, the product can also be purified by column chromatography using ethyl acetate as eluent with similar yields.