Felkin−Anh Stereoselectivity in Cycloadditions of Acetylketene:  Evidence for a Concerted, Pseudopericyclic Pathway

• Published in: Journal of organic chemistry 2000-11, Vol.65 (23), p.7731-7739
• Main Authors: Shumway, William, Ham, Sihyun, Moer, Jessica, Whittlesey, Bruce R, Birney, David M
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo0002644

The cycloadditions of acetylketene with α-chiral aldehydes and ketones are shown to be diastereoselective, forming a tertiary or quaternary chiral center at an acetal or ketal carbon with good stereocontrol. X-ray crystallography of a minor product (5b) shows that the major products (e.g., 4b) are those predicted by the Felkin−Anh model. Transition states are reported at the MP2/6-31G* level for the addition of ethanal to formylketene and at the B3LYP/6-31G* level for the addition of 2-phenylpropanal. The ground-state conformations of the reactants and products are used to rationalize the relative energies and geometries of the transition states without the need to invoke the Cieplak hypothesis. However, chiral substituents on the α-oxoketene show no diastereoselectivity. These experimental and computational results are only consistent with the nearly planar, pseudopericyclic transition state previously proposed.