Stereoselective allylation of ketones: explanation for the unusual inversion of the induced stereochemistry in the auxiliary-mediated crotylation and pentenylation of butanone by DFT calculations

Chemistry : a European Journal
Lutz F TietzeStefan Schmatz

Abstract

Auxiliary-mediated domino crotylations and pentenylations of butanone yield homoallylic ethers with two newly formed stereogenic centers. With our norpseudoephedrine-derived auxiliary, we observed the formation of anti isomers exclusively, and the nature of the major isomer was independent of the substrate double bond geometry. Interestingly, there is a switch in induced selectivity when going from crotylation to pentenylation. Here, we present the computational rationalization for this behavior by identification of the relevant transition states (TSs), the energies of which were determined by using the B3LYP/6-31+G(d) level of theory in combination with the PCM/UAKS method to include the effects exerted by the solvent dichloromethane. To quickly narrow down the number of potentially relevant TSs from the whole set of 288 and 864 TSs for the crotylation and pentenylation, respectively, we employed a screening process based on B3LYP//AM1 energies. The predicted selectivities are in good agreement with experimentally determined ones. Furthermore, the obtained results also facilitate an explanation of the selectivities obtained in hexenylations and heptenylations. Finally, activation energies were determined that account for the s...Continue Reading

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Feb 1, 1996·Chemical Reviews·Lutz F. Tietze
Oct 9, 2002·Angewandte Chemie·Karen M WaltzPatrick J Walsh
Dec 20, 2003·The Journal of Organic Chemistry·John R Huckins, Scott D Rychnovsky
Jul 22, 2004·Journal of the American Chemical Society·Reiko WadaMasakatsu Shibasaki
Oct 20, 2005·Journal of the American Chemical Society·Manabu Wadamoto, Hisashi Yamamoto
Jun 6, 2008·Angewandte Chemie·Lutz F TietzeArne Ringe

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Citations

May 2, 2012·Chemical Society Reviews·Corien de GraaffRomano V A Orru
Nov 20, 2012·Chemical Reviews·Hélène Pellissier

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