Optical Activity of Chiral Epoxides: Influence of Structure & Environment on Intrinsic Chiroptical Response Paul M. Lemler, Clayton L. Craft, & Patrick.

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Presentation transcript:

Optical Activity of Chiral Epoxides: Influence of Structure & Environment on Intrinsic Chiroptical Response Paul M. Lemler, Clayton L. Craft, & Patrick H. Vaccaro Department of Chemistry, Yale University 225 Prospect Street New Haven, CT 06520-8107 USA

Natural Optical Activity A Brief Overview Circular Birefringence (CB) : Non-Resonant Differential Retardation Solution phase optical activity is introduced as an intrinsic property of chiral solute molecule Solvent-solute interactions can drastically modify observed magnitude & sign† Quantitative interpretation of CB necessitates interrogation of solvent-free response. † S. M. Wilson, K.B. Wiberg, M.J. Murphy, and P.H. Vaccaro Chirality 20(3-4), 357-369 (2008).

Cavity Ring-Down Polarimetry P. H. Vaccaro, Chapter 11 in Comprehensive Chiroptical Spectroscopy, eds. N. Berova, et al. (Wiley, Hoboken, NJ, 012).

Systems Currently Being Investigated RG09 Clayton Craft (1S,2S) –Phenylpropylene oxide (PPO) (R)–3–Methyl–2–Aminobutane (MAB) (R) –2–Methylpyrrolidine (MPY) (R)–Styrene oxide (SO) (S)–3,3–Dimethyl–2–Aminobutane (DMAB) (S) –2–Methylpiperidine (MPI) (R)–α–Methylbenzylamine (αMBA) (S)–Glycidol (GLY) Methyl–(2S)–Glycidate (MGly)

Vibrational Contribution to Optical Activity Calculate expectation value for each vibrational quantum state: Determine Boltzmann weight for each quantum state: Compute collective response for thermal ensemble:

Implicit Solvation Model Polarizable Continuum Model Solvent modeled as dielectric continuum surrounding interlocking van der Waals- spheres centered at atomic positions Accurately describes long-range electrostatic solute-solvent interactions Dominated by electrostatic contributions to solvated response, ignoring first-shell interactions which govern short-range interaction terms. Valued and ubiquitously utilized for its computational expedience stemming from reduced degrees of freedom in comparison to explicit models of solvation

Summary and Conclusions Cavity Ring-Down Polarimetry (CRDP) affords a sensitive probe for elucidating dispersive optical activity (CB) under rarefied gas-phase conditions. Solvation can influence optical activity in pronounced and counterintuitive ways, modifying both the magnitude and the sign of response evoked from rigid molecules. Small electronic response of styrene oxide (SO) is perturbed significantly by vibrational contributions and highlights inadequacies of DFT predictions for optical activity. Implicit solvation models are in good accord with PPO behavior, but show less satisfactory agreement with SO response possibly due to vibrational contributions. Future efforts will include molecular dynamics simulations to search for solute-solvent complexes combined with more extensive vibrational-averaging analyses. Supported by U.S. National Science Foundation