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Volumn 75, Issue 24, 2010, Pages 8363-8371

Synthesis and structure of m-terphenyl thio-, seleno-, and telluroethers

Author keywords

[No Author keywords available]

Indexed keywords

ATROPISOMERISM; ATROPISOMERS; BENZYNE; CHALCOGENS; DISELENIDES; ELECTROPHILES; GRIGNARD REAGENT; INTERCONVERSIONS; SINGLE CRYSTAL X-RAY ANALYSIS; SYNTHETIC ROUTES; TE COMPOUNDS; TERPHENYLS; VARIABLE-TEMPERATURE NMR;

EID: 78650379602     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo101299x     Document Type: Article
Times cited : (16)

References (39)
  • 23
    • 78650362028 scopus 로고    scopus 로고
    • Although the peak shapes observed for 1c and 3a can be fitted well using two atropisomers, those observed for 2a are not as well-fitted. A better fit is obtained using three atropisomers but the calculations outlined later in the paper do not support another conformer for 2a
    • Although the peak shapes observed for 1c and 3a can be fitted well using two atropisomers, those observed for 2a are not as well-fitted. A better fit is obtained using three atropisomers but the calculations outlined later in the paper do not support another conformer for 2a.
  • 24
    • 66149121377 scopus 로고    scopus 로고
    • The van der Waals radius for S, Se, and Te is 1.80, 1.90, and 2.06, respectively
    • The van der Waals radius for S, Se, and Te is 1.80, 1.90, and 2.06, respectively: Mantina, M.; Chamberlin, A. C.; Valero, R.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. A 2009, 113, 5806-5812
    • (2009) J. Phys. Chem. A , vol.113 , pp. 5806-5812
    • Mantina, M.1    Chamberlin, A.C.2    Valero, R.3    Cramer, C.J.4    Truhlar, D.G.5
  • 26
    • 0003909854 scopus 로고
    • 2 nd; Wiley: New York
    • Günther, H. NMR Spectroscopy, 2 nd; Wiley: New York, 1992; pp 343.
    • (1992) NMR Spectroscopy , pp. 343
    • Günther, H.1
  • 27
    • 78650316857 scopus 로고    scopus 로고
    • To quantitate this effect, we calculated the potential for the interaction of dimethylsulfide or dimethylselenide, respectively, with a benzene H-atom as depicted. The equilibrium distance was 2.8 Å for S and 3.0 Å for Se. At the transition states for rotation around a lateral phenyl group in 1a the S···H distance is ca. 2.1 Å and in 2a it is 2.3 Å. At these distances the energy is higher by 13.2 kJ/mol in the model complex for X = S and by 16.3 kJ/mol for X = Se. The difference between these two numbers (3.1 kJ/mol) accounts for a large part of the differences in the enthalpies of activation for rotation of a lateral phenyl group in 1a and 2a
    • To quantitate this effect, we calculated the potential for the interaction of dimethylsulfide or dimethylselenide, respectively, with a benzene H-atom as depicted. The equilibrium distance was 2.8 Å for S and 3.0 Å for Se. At the transition states for rotation around a lateral phenyl group in 1a the S···H distance is ca. 2.1 Å and in 2a it is 2.3 Å. At these distances the energy is higher by 13.2 kJ/mol in the model complex for X = S and by 16.3 kJ/mol for X = Se. The difference between these two numbers (3.1 kJ/mol) accounts for a large part of the differences in the enthalpies of activation for rotation of a lateral phenyl group in 1a and 2a.
  • 29
    • 78650345649 scopus 로고    scopus 로고
    • erestingly, House et al. (23) report a minor component in acetate 10b that rapidly interconverts with the syn isomer. They assign the structure of this minor component to the syn isomer with the OAc cis to the aryl methyl groups which equilibrates with the major syn isomer with the OAc trans to the aryl methyl groups. If this assignment for the minor component is correct, then the rotation barrier about the aryl-O bond in 10b is greater than the rotation barriers about the aryl-X bond (X = S, Se, Te) in the substituted and unsubstituted m -terphenyl chalcogenoethers 1-3
    • Interestingly, House et al. (23) report a minor component in acetate 10b that rapidly interconverts with the syn isomer. They assign the structure of this minor component to the syn isomer with the OAc cis to the aryl methyl groups which equilibrates with the major syn isomer with the OAc trans to the aryl methyl groups. If this assignment for the minor component is correct, then the rotation barrier about the aryl-O bond in 10b is greater than the rotation barriers about the aryl-X bond (X = S, Se, Te) in the substituted and unsubstituted m -terphenyl chalcogenoethers 1-3.
  • 32
    • 64549117421 scopus 로고    scopus 로고
    • report a high barrier (Δ G = 38.0 kcal/mol at 140 °C) for racemization of chiral anthraquinone 11. The configurational stability of anthraquinone 11 was ascribed to steric interaction between the methylnaphthyl substituent and anthraquinone carbonyl group. However, this is only remotely related to the systems studied in the present paper
    • Lunazzi, L.; Mancinelli, M.; Mazzanti, A. J. Org. Chem. 2009, 74, 1345-1348 report a high barrier (Δ G = 38.0 kcal/mol at 140 °C) for racemization of chiral anthraquinone 11. The configurational stability of anthraquinone 11 was ascribed to steric interaction between the methylnaphthyl substituent and anthraquinone carbonyl group. However, this is only remotely related to the systems studied in the present paper.
    • (2009) J. Org. Chem. , vol.74 , pp. 1345-1348
    • Lunazzi, L.1    Mancinelli, M.2    Mazzanti, A.3
  • 35
    • 84962382681 scopus 로고    scopus 로고
    • Gaussian, the WP04 functional is invoked by specifying the BLYP keyword and adding iop(3/76=1000001189,3/77=0961409999,3/78=0000109999) to the keyword line
    • Wiitala, K. W.; Hoye, T. R.; Cramer, C. J. J. Chem. Theory Comput. 2006, 2, 1085-1092 In Gaussian, the WP04 functional is invoked by specifying the BLYP keyword and adding iop(3/76=1000001189,3/77=0961409999,3/78=0000109999) to the keyword line.
    • (2006) J. Chem. Theory Comput. , vol.2 , pp. 1085-1092
    • Wiitala, K.W.1    Hoye, T.R.2    Cramer, C.J.3
  • 38
    • 43649108963 scopus 로고    scopus 로고
    • For an overview of these methods, see
    • For an overview of these methods, see: Schwabe, T.; Grimme., S. Acc. Chem. Res. 2008, 41, 569-579
    • (2008) Acc. Chem. Res. , vol.41 , pp. 569-579
    • Schwabe, T.1    Grimme, S.2
  • 39
    • 78650314562 scopus 로고    scopus 로고
    • and Gaussian 09, Revision A.02; Gaussian, Inc.: Wallingford, CT, (for complete reference, see Supporting Information)
    • Frisch, M. J. et al. Gaussian 03, Revision E.01 and Gaussian 09, Revision A.02; Gaussian, Inc.: Wallingford, CT, 2003, (for complete reference, see Supporting Information).
    • (2003) Gaussian 03, Revision E.01
    • Frisch, M.J.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.