Cyclophanes as Templates in Stereoselective Synthesis

Rozenberg, V. I.; Сергеева, Е. В.; Hopf, Henning

doi:10.1002/3527603964.ch17

Cited by 76 publications

(30 citation statements)

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“…A stereospecific synthesis of [6]paracyclophane-8-carboxylic acid (2) was reported, and its CD spectrum was compared with that of [8]paracyclophane-10-carboxylic acid (3, R = CO 2 H) [17]. The former afforded a pair of bisignate CD patterns in the 200-400 nm region, while only a pair of Cotton effect peaks of the same sign were observed for the latter.…”

Section: [N]paracyclophanesmentioning

confidence: 90%

“…The observed Cotton effects were slightly weaker than those observed for [6]paracyclophane 2 [18]. The CD spectrum of 9,12-dimethyl-4-oxa [7]paracyclophane 5 was measured and compared with the theoretical one calculated with the DFT/SCI method.…”

Section: [N]paracyclophanesmentioning

confidence: 95%

“…[6]Paracyclophane (2) is one of the most strained cyclophanes, and its boat-type deformation of the benzene ring led to the red-shift of ca. 30 nm in its UV and CD spectra.…”

Section: [N]paracyclophanesmentioning

confidence: 99%

“…Recent advances and applications in this area have been reviewed [5,6]. The synthesis of heterocyclic compounds based on [2.2]paracyclophane architecture, where the long-distance electronic communication and the planar chirality play significant roles in their application, has also been reported recently [7].…”

Section: Introductionmentioning

confidence: 99%

“…For ease of viewing, one of the enantiomers is drawn in 3D to underline the stereochemistry (i.e., R p /S p , M/P, or aR/aS), even if both of the enantiomers were studied in the original literature. Stereochemical notation of the chiral cyclophanes has been summarized in reviews [5,6]. Literature dealing with or commenting on the chiral cyclophanes but not reporting on the experimental CD spectra are excluded throughout this review.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Recent Theoretical and Experimental Advances in the Electronic Circular Dichroisms of Planar Chiral Cyclophanes

Mori

Inoue

2010

Electronic and Magnetic Properties of Chiral Molecules and Supramolecular Architectures

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The chiroptical properties, such as electronic and vibrational circular dichroism and optical rotation, of planar chiral cyclophanes have attracted much attention in recent years. Although the chemistry of cyclophanes has been extensively explored for more than 60 years, the studies on chiral cyclophanes are rather limited. Experimentally, the use of chiral stationary phases in HPLC becomes more popular and facilitates the enantiomer separation of chiral cyclophanes of interest. Almost all chiral cyclophanes can be readily separated, in analytical and preparative scales, most typically on a Daicel OD type column, which is based on cellulose tris(3,5-dimethylphenylcarbamate). The CD spectra of chiral cyclophanes are unique in their fairly large, significantly coupled Cotton effects observed in all the 1 B b , 1 L a , and 1 L b band regions. Theoretically, the time-dependent density functional theory, or TD-DFT, method becomes a cost-efficient, yet accurate, theoretical method to reproduce the electronic circular dichroisms and the absorption spectra of a variety of cyclophanes. The direct comparison of the experimental CD spectra with the theoretical ones readily leads to the unambiguous assignment of the absolute configuration of cyclophanes. In addition, the analysis of configuration interaction and molecular orbitals allows detailed interpretation of the electronic transitions and Cotton effects in the UV and CD spectra. Through the study of the CD spectra of chiral cyclophanes as model systems, the effects of intra-and intermolecular interactions on the chiroptical properties of molecules can be explored, and the results thus obtained are valuable in comprehensively elucidating the structure-chiroptical property relationship. In this review the recent progress in experimental and theoretical investigations of the electronic CD spectra of chiral cyclophanes is discussed.

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Section: [N]paracyclophanesmentioning

confidence: 90%

Section: [N]paracyclophanesmentioning

confidence: 95%

“…[6]Paracyclophane (2) is one of the most strained cyclophanes, and its boat-type deformation of the benzene ring led to the red-shift of ca. 30 nm in its UV and CD spectra.…”

Section: [N]paracyclophanesmentioning

confidence: 99%