Theoretical and experimental investigations of circular dichroism and absolute configuration determination of chiral anthracene photodimers.

Substituted anthracenes photodimerize to stereoisomeric [4 + 4] cyclodimers, some of which are inherently chiral. Recent supramolecular photochirogenic studies enabled the efficient preparation of specific stereoisomers, the absolute configurations of which should reflect the chiral environment of supramolecular host or scaffold employed but have not been determined, hindering detailed mechanistic elucidation and further host/scaffold design. In this study, we performed the combined experimental and state-of-the-art theoretical analyses of the circular dichroism spectra of chiral cyclodimers of 2-anthracenecarboxylic and 2,6-anthracenedicarboxylic acids to reveal the configurational and molecular orbital origin of the Cotton effects observed, and unambiguously determined the absolute configurations of these chiral cyclodimers. The present results allow us to directly correlate the enantiotopic face-selectivity upon photocyclodimerization with the absolute configuration of the cyclodimer derived therefrom and also to precisely elucidate the chiral arrangement of two cyclodimerizing anthracenes.

[1]  K. Ichimura,et al.  Regio- and stereoselective photodimerization of anthracene derivatives included by cyclodextrins , 1987 .

[2]  S. Shinkai,et al.  An organogel system can control the stereochemical course of anthracene photodimerization. , 2009, Chemical communications.

[3]  Masaki Nishijima,et al.  Highly enantiomeric supramolecular [4 + 4] photocyclodimerization of 2-anthracenecarboxylate mediated by human serum albumin. , 2007, Journal of the American Chemical Society.

[4]  Stefan Grimme,et al.  Accurate description of van der Waals complexes by density functional theory including empirical corrections , 2004, J. Comput. Chem..

[5]  Yi-tao Yang,et al.  Theoretical analysis of the individual contributions of chiral arrays to the chiroptical properties of tris-diamine ruthenium chelates. , 2009, Journal of the American Chemical Society.

[6]  Masaki Nishijima,et al.  Supramolecular complexation and enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid with 4-aminoprolinol derivatives as chiral hydrogen-bonding templates. , 2009, The Journal of organic chemistry.

[7]  Y. Ko,et al.  Highly stereoselective photocyclodimerization of alpha-cyclodextrin-appended anthracene mediated by gamma-cyclodextrin and cucurbit[8]uril: a dramatic steric effect operating outside the binding site. , 2008, Journal of the American Chemical Society.

[8]  Prasad L Polavarapu,et al.  Optical rotation: recent advances in determining the absolute configuration. , 2002, Chirality.

[9]  T. Daniel Crawford,et al.  Ab initio calculation of molecular chiroptical properties , 2006 .

[10]  J. Autschbach,et al.  Tuned Range-Separated Time-Dependent Density Functional Theory Applied to Optical Rotation. , 2012, Journal of chemical theory and computation.

[11]  N. Harada,et al.  Circular dichroic power of chiral triptycenes , 1980 .

[12]  Cheng Yang,et al.  Supramolecular enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate mediated by capped gamma-cyclodextrins: critical control of enantioselectivity by cap rigidity. , 2008, The Journal of organic chemistry.

[13]  S. Grimme,et al.  Density functional theory with dispersion corrections for supramolecular structures, aggregates, and complexes of (bio)organic molecules. , 2007, Organic & biomolecular chemistry.

[14]  B. Gibb,et al.  A hydrophobic nanocapsule controls the photophysics of aromatic molecules by suppressing their favored solution pathways. , 2005, Journal of the American Chemical Society.

[15]  Micah L. Abrams,et al.  Chiroptical properties of (R)-3-chloro-1-butene and (R)-2-chlorobutane. , 2007, The journal of physical chemistry. A.

[16]  Thomas Bondo Pedersen,et al.  Coupled cluster response calculation of natural chiroptical spectra , 1999 .

[17]  K. Mikkelsen,et al.  A coupled cluster study of the oriented circular dichroism of the n→π∗ electronic transition in cyclopropanone and natural optical active related structures , 2004 .

[18]  Motonori Watanabe,et al.  Optical resolution, absolute configuration, and chiroptical properties of three-layered [3.3]paracyclophane. , 2008, The Journal of organic chemistry.

[19]  Kieron Burke,et al.  Basics of TDDFT , 2006 .

[20]  Howard E. Smith.  Chiroptical Properties of the Benzene Chromophore. A Method for the Determination of the Absolute Configurations of Benzene Compounds by Application of the Benzene Sector and Benzene Chirality Rules. , 1998, Chemical reviews.

[21]  H. Ikeda,et al.  Template-assisted stereoselective photocyclodimerization of 2-anthracenecarboxylic acid by bispyridinio-appended gamma-cyclodextrin. , 2005, The Journal of organic chemistry.

[22]  Andreas Dreuw,et al.  Single-reference ab initio methods for the calculation of excited states of large molecules. , 2005, Chemical reviews.

[23]  Jesús A. Varela,et al.  Assignment of the absolute configuration of (+)-5,5′,6,6′-tetrahydro-7,7′-spiro[7H-cyclopenta[b]pyridine], a new inherently chiral spiropyridine, by a nonempirical analysis of its circular dichroism spectrum , 2006 .

[24]  Christof Hättig,et al.  Transition moments and excited-state first-order properties in the coupled-cluster model CC2 using the resolution-of-the-identity approximation , 2002 .

[25]  M. Maeda,et al.  Bio-supramolecular photochirogenesis with molecular chaperone: enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate mediated by prefoldin , 2010, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[26]  S. Grimme,et al.  Quantum chemical study on the circular dichroism spectra and specific rotation of donor-acceptor cyclophanes. , 2007, The journal of physical chemistry. A.

[27]  A. Castellan,et al.  Photodimerization of anthracenes in fluid solutions: (part 2) mechanistic aspects of the photocycloaddition and of the photochemical and thermal cleavage , 2001 .

[28]  Poul Jørgensen,et al.  The second-order approximate coupled cluster singles and doubles model CC2 , 1995 .

[29]  M. E. Casida.  Time-Dependent Density Functional Response Theory for Molecules , 1995 .

[30]  Tadashi Mori,et al.  Absolute configuration of chiral [2.2]paracyclophanes with intramolecular charge-transfer interaction. Failure of the exciton chirality method and use of the sector rule applied to the cotton effect of the CT transition. , 2005, Journal of the American Chemical Society.

[31]  Stefan Grimme,et al.  Systematic Investigation of Modern Quantum Chemical Methods to Predict Electronic Circular Dichroism Spectra , 2003 .

[32]  Yoshihisa Inoue,et al.  Chirality-sensing supramolecular systems. , 2008, Chemical reviews.

[33]  Robert G. Parr,et al.  A Semi‐Empirical Theory of the Electronic Spectra and Electronic Structure of Complex Unsaturated Molecules. II , 1953 .

[34]  John R. Platt,et al.  Classification of Spectra of Cata-Condensed Hydrocarbons , 1949 .

[35]  Yu Liu,et al.  Catalytic enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid mediated by a non-sensitizing chiral metallosupramolecular host. , 2009, Angewandte Chemie.

[36]  T. Crawford,et al.  Ab initio optical rotatory dispersion and electronic circular dichroism spectra of (S)-2-chloropropionitrile. , 2006, The journal of physical chemistry. A.

[37]  Stefan Grimme,et al.  Calculation of electronic circular dichroism spectra with time-dependent double-hybrid density functional theory. , 2009, The journal of physical chemistry. A.

[38]  A. Dreuw,et al.  The Art of Choosing the Right Quantum Chemical Excited‐State Method for Large Molecular Systems , 2011 .

[39]  Y. Inoue,et al.  Supramolecular catalysis of the enantiodifferentiating [4 + 4] photocyclodimerization of 2-anthracenecarboxylate by gamma-cyclodextrin. , 2003, Journal of the American Chemical Society.

[40]  A. Castellan,et al.  Photodimerization of anthracenes in fluid solution:structural aspects , 2000 .

[41]  H. Becker.  Unimolecular photochemistry of anthracenes , 1993 .

[42]  David M. Collard,et al.  Cross-Linking and Modification of Poly(ethylene terephthalate-co-2,6-anthracenedicarboxylate) by Diels-Alder Reactions with Maleimides , 1999 .

[43]  R. Broene,et al.  The synthesis of circumanthracene , 1991 .

[44]  G. Bringmann,et al.  Total synthesis of the N,C-coupled naphthylisoquinoline alkaloids ancistrocladinium A and B and related analogues. , 2010, Journal of the American Chemical Society.

[45]  S. Grimme.  Accurate calculation of the heats of formation for large main group compounds with spin-component scaled MP2 methods. , 2005, The journal of physical chemistry. A.

[46]  Keiko Ideta,et al.  Synthesis, structure, and transannular pi-pi interaction of three- and four-layered [3.3]paracyclophanes. , 2008, The Journal of organic chemistry.

[47]  Dennis Sheberla,et al.  Products and mechanism of acene dimerization. A computational study. , 2011, Journal of the American Chemical Society.

[48]  A. Dreuw,et al.  Molecular mechanism of uncaging CO2 from nitrophenylacetate provides general guidelines for improved ortho-nitrobenzyl cages. , 2011, Chemphyschem : a European journal of chemical physics and physical chemistry.

[49]  J. Pople,et al.  Electron interaction in unsaturated hydrocarbons , 1953 .

[50]  A. Jyo,et al.  Photochemical ligation of DNA conjugates through anthracene cyclodimer formation and its fidelity to the template sequences. , 2004, Journal of the American Chemical Society.

[51]  Masaki Nishijima,et al.  Supramolecular photochirogenesis with biomolecules. Mechanistic studies on the enantiodifferentiation for the photocyclodimerization of 2-anthracenecarboxylate mediated by bovine serum albumin. , 2007, The Journal of organic chemistry.