Efficient remote axial-to-central chirality transfer in enantioselective SmI2-mediated reductive coupling of aldehydes with crotonates of atropisomeric 1-naphthamides

The Journal of Organic Chemistry
Yan ZhangWei-Min Dai

Abstract

Control of enantioselectivity by remote amide conformation has been studied in SmI2-mediated reductive coupling of aldehydes with the crotonates possessing different 2-substituted 8-methoxy-1-naphthamides. The enantiomers of atropisomeric 8-methoxy-1-naphthamides were prepared through a chemical resolution process, and their absolute stereochemistry was determined by X-ray crystal structural analysis. It was found that the linkage between crotonate and the C2 position of 8-methoxy-1-naphthamides remarkably influenced the efficiency of remote chirality transfer originated from the amide conformation. Among the four crotonates examined, the one derived from 2-hydroxy-8-methoxy-1-naphthamide reacted with pentanal to afford the highest ee of > 99% for the cis-gamma-butyrolactone and in 90% combined yield with a cis/trans ratio of 90:10. We developed a new procedure for attaching the chiral crotonate via the C8 oxygen to a Rink amide resin under mild conditions and obtained the same level of highly remote axial-to-central chirality transfer in the solid-phase reaction.

References

Nov 9, 2002·Organic Letters·Hernando J OlivosThomas Kodadek

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Citations

Apr 23, 2011·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Danilo Mirizzi, Maurizio Pulici
Jan 23, 2008·Chemical Communications : Chem Comm·Jonathan ClaydenMadeleine Helliwell
Apr 11, 2008·The Journal of Organic Chemistry·Jonathan ClaydenElizabeth Moir
Apr 25, 2014·Chemical Reviews·Michal SzostakDavid J Procter
Apr 13, 2019·Organic Letters·Simone CrottiGiorgio Bencivenni

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