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Volumn 71, Issue 21, 2006, Pages 8212-8218

Resolution, enantiomerization kinetics, and chiroptical properties of 7,7′-dihydroxy-8,8′-biquinolyl

Author keywords

[No Author keywords available]

Indexed keywords

ENANTIOMERIZATION; ENANTIOMORPHIC ATROPISOMERS; STEREOCHEMICAL CONFIGURATIONS;

EID: 33750025856     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo061608e     Document Type: Article
Times cited : (28)

References (75)
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    • Mascarelli was the first to suggest the possibility of optical isomerism in biquinolyl-type compounds, a hypothesis later verified by the work of Crawford: (a) Mascarelli, L. Gazz. Chim. Ital. 1928, 58, 627.
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    • The following potential resolving agents for (±)-6 were surveyed unsuccessfully: (+)-camphor sulfonic acid, CuCl/(-)-sparteine complex, and benzylcinchonidinium chloride. For recent applications of the latter two agents in resolution work, see: (a) Zhang, Y.; Yeung, S.-M.; Wu, H.; Heller, D. P.; Wu, C.; Wulff, W. D. Org. Lett. 2003, 5, 1813.
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    • erratum
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    • Prefix descriptors, lk (like) and ul (unlike), refer to configurational relationships between the stereogenic axis and the C1 position of the menthyl moiety within diastereoisomers of 9. For discourse on this and related terminology, see: Seebach, D.; Prelog, V. Angew. Chem., Int. Ed. Engl. 1982, 21, 654.
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    • note
    • Diastereoisomers (-)-lk-9 and (+)-ul-9 could not be separated by simple fractional recrystallization, and flash column chromatographic separation proved much inferior to the HPLC-based method.
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    • The angle between the two intersecting least-squares quinolyl ring planes of (-)-lk-9 is 117.7°, as compared to only 104.5° for the same property exhibited in the solid state by (±)-6·2MeOH (see ref 15). Both (-)-lk-9 and (±)-6 are more transoid than crystalline forms of either (±)-BINOL or (+)-(aR)-BINOL (angles between intersecting naphthyl ring planes are 90.6° and 101.7°. respectively), see: Mori, K.; Masuda, Y.; Kashino, S. Acta Crystallogr. 1993, C49, 1224.
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    • note
    • For example, (+)-lk-9 with dr = 75:25 (about axis) was subjected to hydrolysis, and the resulting sample of (+)-(aR)-6 was immediately rederivatized by treatment with excess (-)-8 to yield (+)-lk-9 with dr = 70:30. Conversion for both steps was essentially quantitative.
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    • 2O, etc.), polarimeter readings were taken from dilute solutions of 6 in aqueous base (1 M NaOH). Optical rotation values in this medium were observed to be invariant at ambient temperature over several hours (20 h).
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    • note
    • H (ul-9) = 8.80 (1H, dd, J = 4.1, 1.6 Hz, C2/2′-H).
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    • note
    • On occasion, crystals of 6 would form during enantiomerization experiments, and, in such cases, non-first-order decay in %ee was typically observed. Kinetic data collected from runs in which any inhomogeneity in the reaction mixture was observed were therefore discarded.
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    • note
    • ‡).
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    • Satisfactory transition state structures for the enantiomerization of 6 could not be located using density functional theory (B3LYP/6-31G*, Spartan); however, semiempirical calculations at the AM1 level identified transition states exhibiting appropriate single negative eigenvalues (see the Supporting Information for details). Analogous AM1 computations have been demonstrated to give good results in the determination of rotation barriers for 1,1-binaphthyl derivatives, see: Kranz, M.; Clark, T.; Schleyer, P. v. R. J. Org. Chem. 1993, 58, 3317.
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    • For the quantitative determination of the dihedral angle of 2,2′-homosubstituted 1,1′-binaphthyls by CD-spectral analysis, see: Di Bari, L.; Pescitelli, G.; Salvadori, P. J. Am. Chem. Soc. 1999, 121, 7998.
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    • For application of the exciton chirality method to the assignment of absolute configuration, see: (a) Harada, N.; Nakanishi, K. Acc. Chem. Res. 1972, 5, 257.
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    • The results of electronic and vibrational circular dichroism analysis place the mean dihedral angle for BINOL between 85° and 100°, see, CD: (a) Hanazaki, I.; Akimoto, H. J. Am. Chem. Soc. 1972, 94, 4102.
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    • note
    • Hirao and co-workers reported the assignment of absolute configuration to a series of 1,1′-biisoquinolyls based on CD-spectral analysis; see ref 10d.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.