Chiral Action at a Distance: Remote Substituent Effects on the Optical Activity of Calyculins A and B

Organic Letters

Volumn 2, Issue 11, 2000, Pages 1509-1512

  Kondru, Rama K ^a   Beratan, David N ^a   Friestad, Gregory K ^b   Smith III, Amos B ^c   Wipf, Peter ^a  

^a UNIVERSITY OF PITTSBURGH   (United States)

^b UNIVERSITY OF VERMONT   (United States)

^c UNIVERSITY OF PENNSYLVANIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BIOLOGICAL FACTOR; CALYCULIN A; CALYCULIN B; CARCINOGEN; ENZYME INHIBITOR; ORGANOPHOSPHATE; OXAZOLE DERIVATIVE; PHOSPHOPROTEIN PHOSPHATASE; VASOCONSTRICTOR AGENT;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; CONFORMATION; DRUG ANTAGONISM; OPTICAL ROTATION; STEREOISOMERISM; THERMODYNAMICS;

BIOLOGICAL FACTORS; CARCINOGENS; ENZYME INHIBITORS; MODELS, MOLECULAR; MOLECULAR CONFORMATION; OPTICAL ROTATION; OXAZOLES; PHOSPHOPROTEIN PHOSPHATASE; PHOSPHORIC ACID ESTERS; STEREOISOMERISM; THERMODYNAMICS; VASOCONSTRICTOR AGENTS;

EID: 0034199932     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol005634p     Document Type: Article

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26. The lowest energy conformers obtained by Monte Carlo sampling were minimized at every step and compared to see if the newly obtained structure was duplicated. If so, the duplicated structure was ignored. Only unique structures were retained. Low energy structures were usually chosen from a Monte Carlo sampling of 3000 conformations: each new conformation was minimized using a 3000-step energy minimization iteration method, forcing all the newly found structures to be fully relaxed. Taking the origin as the center of mass in the CADPAC calculations is expected to avoid substantive gauge origin dependent results for structures of this size (see ref 5g). Both in the X-ray and the MM2* (MacroModel) minimized structures as well as in ab initio calculations at the HF/6-31G**, DFT/ B3LYP/6-31G*, MP2/6-31G, and MP2/6-31G* levels, the tetraene moiety is slightly bent, with only a few degrees of variation in the torsional angles between the different methods. For comparison, a complete listing of the computed ground state and the X-ray torsional angles can be found in the Supporting Information. Furthermore, while empirical force fields are poorly suited for the calculation of vibrational spectra of polyene chains (Schettino, V.; Gervasio, F. L.; Cardini, G.; Salvi, P. R. J. Chem. Phys. 1999, 110, 3241), conformational and torsional energies of conjugated compounds determined with MM2* (MacroModel) were found to provide excellent agreement with experimental values (Gundertofte, K.; Liljefors, T.; Norrby, P.-O.; Pettersson, I. J. Comput. Chem. 1996, 17, 429).
27. The lowest energy conformers obtained by Monte Carlo sampling were minimized at every step and compared to see if the newly obtained structure was duplicated. If so, the duplicated structure was ignored. Only unique structures were retained. Low energy structures were usually chosen from a Monte Carlo sampling of 3000 conformations: each new conformation was minimized using a 3000-step energy minimization iteration method, forcing all the newly found structures to be fully relaxed. Taking the origin as the center of mass in the CADPAC calculations is expected to avoid substantive gauge origin dependent results for structures of this size (see ref 5g). Both in the X-ray and the MM2* (MacroModel) minimized structures as well as in ab initio calculations at the HF/6-31G**, DFT/ B3LYP/6-31G*, MP2/6-31G, and MP2/6-31G* levels, the tetraene moiety is slightly bent, with only a few degrees of variation in the torsional angles between the different methods. For comparison, a complete listing of the computed ground state and the X-ray torsional angles can be found in the Supporting Information. Furthermore, while empirical force fields are poorly suited for the calculation of vibrational spectra of polyene chains (Schettino, V.; Gervasio, F. L.; Cardini, G.; Salvi, P. R. J. Chem. Phys. 1999, 110, 3241), conformational and torsional energies of conjugated compounds determined with MM2* (MacroModel) were found to provide excellent agreement with experimental values (Gundertofte, K.; Liljefors, T.; Norrby, P.-O.; Pettersson, I. J. Comput. Chem. 1996, 17, 429).
28. D units (see Supporting Information of ref 2a). DEIPS = diethylisopropylsilyl, TBS = tert-butyldimethylsilyl, TMS = trimethylsilyl. (Equation Presented)
29. For details of this methodology, see: Kondru, R. K.; Wipf, P.; Beratan, D. N., manuscript in preparation.
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34. We hypothesize that the tetraene unit serves as a topological coupler for the transition dipole moment interaction. Related effects of polyunsaturated chains have been observed, for example, for electron spin coupling (Tomioka, H.; Hattori, M.; Hirai, K.; Sato, K.; Shiomi, D.; Takui, T.; Itoh, K. J. Am. Chem. Soc. 1998, 120, 1106) and radiationless electronic energy transfer (Jensen, K. K.; van Berlekom, S. B.; Kajanus, J.; Mårtensson, J.; Albinsson, B. J. Phys. Chem. A 1997, 101, 2218).
35. We hypothesize that the tetraene unit serves as a topological coupler for the transition dipole moment interaction. Related effects of polyunsaturated chains have been observed, for example, for electron spin coupling (Tomioka, H.; Hattori, M.; Hirai, K.; Sato, K.; Shiomi, D.; Takui, T.; Itoh, K. J. Am. Chem. Soc. 1998, 120, 1106) and radiationless electronic energy transfer (Jensen, K. K.; van Berlekom, S. B.; Kajanus, J.; Mårtensson, J.; Albinsson, B. J. Phys. Chem. A 1997, 101, 2218).