Solvent-Dependent Stereoselectivity in a Still−Wittig Rearrangement:  An Experimental and ab Initio Study

The Still−Wittig rearrangement gave opposite selectivities for (Z:E)-alkenes in THF (3:1) vs toluene (1:3) in the synthesis of serine−proline dipeptide amide isosteres. Four transition states leading to (Z)-and (E)-alkenes with THF and without (representing toluene) were identified by ab initio calc...

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Bibliographic Details
Published in:Organic letters 2001-06, Vol.3 (12), p.1789-1791
Main Authors: Hart, Scott A, Trindle, Carl O, Etzkorn, Felicia A
Format: Article
Language:English
Subjects:
Dipeptides - chemical synthesis
Solvents - chemistry
Stereoisomerism
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Summary:The Still−Wittig rearrangement gave opposite selectivities for (Z:E)-alkenes in THF (3:1) vs toluene (1:3) in the synthesis of serine−proline dipeptide amide isosteres. Four transition states leading to (Z)-and (E)-alkenes with THF and without (representing toluene) were identified by ab initio calculations at the 3-21G* level. The calculated (Z:E)-ratios with THF (4.7:1) and without THF (1:3.2) suggested that the transition state geometries and energies were well-represented by the calculations.
ISSN:1523-7060
1523-7052
DOI:10.1021/ol015764d