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Hyperconjugation Effect in the Conformational Preference of Cyclohexene-Based β-Amino Acids
Jieun Lee1, Minseok Oh1, Seonho Shin1
1Department of Chemistry, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 03722, Republic of Korea.
None:
We report the conformational preferences of two cyclohexene-based cyclic β-amino acids in unnatural peptide helices. cis-2-Aminocyclohex-4-enecarboxylic acid (cis-4-ACHE) can adopt two local conformations that promote both right- and left-handed helical folding. In contrast, cis-2-aminocyclohex-3-enecarboxylic acid (cis-3-ACHE) favors a single local conformation with pseudoaxial NH and pseudoequatorial CO groups. NBO analysis reveals that this conformational preference of cis-3-ACHE is attributed to hyperconjugation between the π-orbital of the C = C bond and the empty σ* orbital of the C-N bond.
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