Density function theory absolute configurations

Stephens PJ, Pan JJ, Krohn K. Determination of the Absolute Configurations of Pharmacological Natural Products via Density Functional Theory Calculations of Vibrational Circular Dichroism The New Cytotoxic Iridoid Piismatomerin. Journal of Organic Chemistry 2007 72(20) 7641-7649. 

P.J. Stephens et al., Determination of absolute configuration using optical rotation calculated using density functional theory. Org. Lett. 4, 4595-4598 (2002)... 

Keywords Absolute configuration and conformation determinations Density functional theory Induced solvent chirality Transient VCD measurements Vibrational circular dichroism... 

Yang GC, Ha T, Fan E et al (2010) Determination of the absolute configurations of synthetic daunorubicin analogues using vibrational circular dichroism spectroscopy and density functional theory. Chirality 22 734—743... 

Stephens, R J. McCaim, D. M. Cheeseman, J. R. Frisch, M. J. Determination of absolute configurations of chiral molecules using ab initio time-dependent density functional theory calculations of optical rotation how reliable are absolute configurations obtained for molecules with small rotations , Chirality 2005,17, S52-S64. 

Mennucci, B. Claps, M. Evidente, A. Rosini, C. Absolute configuration of natural cyclohexene oxides by time dependent density functional theory calculation of the optical rotation the absolute configuration of (-)-sphaeropsidone and (-)-episphaeropsidone revised, J. Org. Chem. 2007, 72, 6680-6691. 

Stephens, P. J. Pan, J. J. Krohn, K. Determination of the absolute configurations of pharmacological natural products via density functional theory calculations of vibrational circular dichroism the bew cytotoxic iridoidprismatomerin, / Org. Chem. 2007, 72, 7641-7649. 

One prominent member of this class of natural products is diversonol (185), which was isolated by Turner in 1978 [128]. Its absolute configuration was determined by Krohn et al. [129] using CD spectroscopy and time dependent density functional theory calculations for electronic circular dichroism (TDDFT ECD) calculations. As discussed in Chapter 14.2, Erase et al. [71, 72] published the first enantioselective synthesis of 185 in 2011 using an anionic domino process. 

The experimental and simulated IR and VCD spectra of 1-azabicyclo-[3.1,0]hexane 17 are shown in Figure The prominent features near 1200 cm-i and 1300 cm clearly establish the absolute configuration of the bicyclic ring skeleton. The investigation of 17 represents the first application of density functional theory for the determination of a molecular force field for VCD calculations. lO" ... 

Determination of Absolute Configurations of Chiral Molecules Using Ab Initio Time-Dependent Density Functional Theory Calculations of Optical Rotation How Reliable are Absolute Configurations Obtained for Molecules with Small Rotations ... 

The stereochemical assignment of chiral pharmaceutical compounds has received great interest in the last years. As mentioned, the NMR methodology is based on substrate derivatization with two enantiomers of a suitable chiral reagent and the comparison of the NMR spectra of the resulting pair of diastereomers. The preference of the latter for a specific conformation leads to a variation of the chemical shift of the substituents of the stereogenic carbon of the substrate, which can be directly related to its absolute configuration. Theoretical methods (molecular mechanics, semiempirical, or density functional theory [DFT]) may be used to support the conformational differentiation. 

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