Direct asymmetric epoxidation of aldehydes using catalytic amounts of enantiomerically pure sulfides

Journal of the American Chemical Society

Volumn 118, Issue 29, 1996, Pages 7004-7005

  Aggarwal, Varinder K ^a   Ford, J Gair ^a   Thompson, Alison ^a   Jones, Ray V H ^b   Standen, Mike C H ^b  

^a UNIVERSITY OF SHEFFIELD   (United Kingdom)

^b ASTRAZENECA   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; SULFIDE;

ARTICLE; ENANTIOMER; ENZYME ACTIVITY; EPOXIDATION; MOLECULAR INTERACTION; STEREOCHEMISTRY;

EID: 0029900606     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961144+     Document Type: Article

References (38)

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33. Durst reported that the benzylide of 2 reacted with benzaldehyde to give stilbene oxide with >96% ee. The enantioselectivity we obtained in our catalytic cycle was significantly lower (72% ee), and so we repeated Durst's original work but obtained only 71% ee. We have measured our ee's by chiral HPLC using a diode array detector to take a UV trace of the enantiomers as they elute. The UV traces of the two peaks were superimposable. Durst's ee's were determined by NMR using Eu shift reagents.
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36. (a) Using stoichiometric amounts of sulfide 3b, high yield (90%) and high enantioselectivity (93% ee) were obtained with benzaldehyde, but with 0.2 equiv of sulfide a slightly lower yield (73%) but the same enantioselectivity was obtained. To obtain reasonable yields when using substoichiometric amounts of sulfide, it was found necessary to conduct reactions at the same effective concentration of sulfide. This presumably resulted in similar rates of ylide formation and reaction with the aldehyde and therefore allowed the sulfide to be returned and recycled at the same rate as that of the stoichiometric process.
37. 2 (0.05 mmol), and the aldehyde (1 mmol) in dichloromethane (0.5 mL) under nitrogen was added a solution of phenyldiazomethane (1.5 mmol in 0.5 mL of dichloromethane) at room temperature over a period of 3 h using a syringe pump. After the solution was stirred for an additional I h, the solvent was removed in vacuo and the residue was chromatographed on silica gel.
38. 5c