Hydroacylation is a useful synthetic method, allowing an aldehyde and alkene to form a ketone. Experimental research has shown that rhodium(I)-BINAP complex catalyzed hydroacylation of vinyl benzaldehyde follows strict enantioselectivity and substitution effects. Through use of M05-2X density functional, the cause of the substitution effects was determined by analyzing the mechanism of the reaction in three scenarios: unsubstituted alkene, internal methyl substitution for R<sup>1</sup>, and terminal methyl substitution for R<sup>2</sup>. By constructing potential energy surfaces, these three scenarios were compared to determine that the barrier for C-C bond formation for the internal substitution is favored over the terminal substitution by a difference of 7.9 kcal/mol. Both enantiomeric pathways were also analyzed to determine the cause of enantioselectivity.

Enantioselectivity and substitution effects in rhodium catalyzed intramolecular hydroacylation

249th National Meeting (2015)

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