Structural determinations by circular dichroism spectra analysis using coupled oscillator methods: An update of the applications of the DeVoe polarizability model

Chirality

Volumn 16, Issue 7, 2004, Pages 422-451

  Superchi, Stefano ^a   Giorgio, Egidio ^a   Rosini, Carlo ^a  

^a UNIVERSITY OF BASILICATA   (Italy)

Author keywords

Absolute configuration; Chiroptical methods; Conformational analysis; Exciton coupling; Optical activity

Indexed keywords

INORGANIC COMPOUND; ORGANIC COMPOUND;

CHIRALITY; CIRCULAR DICHROISM; CONFORMATION; ELECTRIC ACTIVITY; MODEL; OPTICAL ROTATION; OSCILLATOR; POLARIZATION; PRIORITY JOURNAL; REVIEW; STEREOCHEMISTRY;

EID: 3242657163     PISSN: 08990042     EISSN: None     Source Type: Journal    
DOI: 10.1002/chir.20056     Document Type: Review

References (99)

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10. Argemonine: Mason SF, Vane GW, Whitehurst JS. Circular dichroism and absolute configuration of argemonine. Tetrahedron 1967;23: 4087-4094. Bulbocapnine: Mason SF. The application of CD measurements to the non-empirical determination of absolute configuration. In: Bonnet R, Davies JG, editors. Some newer physical methods in structural chemistry. London: United Trade Press; 1967. p 149-158. Mason SF, Brickell WS, Roberts DR. π-SCF studies of the circular dichroism and electronic spectra of alkaloids containing the aniline chromophore. Stereochemical configuration of calycanthine and caracurine II. J Chem Soc (B) 1971:691-695. Tröger base: Mason SF, Vane GW, Wells RJ, Whitehurst JS. Circular dichroism and absolute configuration of Tröger's base. J Chem Soc (B) 1967:553-556. Transstilbene oxide: Gottarelli G, Mason SF, Torre G. Circular dichroism and absolute configuration of (+)-trans-sfilbene oxide. J Chem Soc (B) 1970:1349-1353.
11. Argemonine: Mason SF, Vane GW, Whitehurst JS. Circular dichroism and absolute configuration of argemonine. Tetrahedron 1967;23: 4087-4094. Bulbocapnine: Mason SF. The application of CD measurements to the non-empirical determination of absolute configuration. In: Bonnet R, Davies JG, editors. Some newer physical methods in structural chemistry. London: United Trade Press; 1967. p 149-158. Mason SF, Brickell WS, Roberts DR. π-SCF studies of the circular dichroism and electronic spectra of alkaloids containing the aniline chromophore. Stereochemical configuration of calycanthine and caracurine II. J Chem Soc (B) 1971:691-695. Tröger base: Mason SF, Vane GW, Wells RJ, Whitehurst JS. Circular dichroism and absolute configuration of Tröger's base. J Chem Soc (B) 1967:553-556. Transstilbene oxide: Gottarelli G, Mason SF, Torre G. Circular dichroism and absolute configuration of (+)-trans-sfilbene oxide. J Chem Soc (B) 1970:1349-1353.
12. Argemonine: Mason SF, Vane GW, Whitehurst JS. Circular dichroism and absolute configuration of argemonine. Tetrahedron 1967;23: 4087-4094. Bulbocapnine: Mason SF. The application of CD measurements to the non-empirical determination of absolute configuration. In: Bonnet R, Davies JG, editors. Some newer physical methods in structural chemistry. London: United Trade Press; 1967. p 149-158. Mason SF, Brickell WS, Roberts DR. π-SCF studies of the circular dichroism and electronic spectra of alkaloids containing the aniline chromophore. Stereochemical configuration of calycanthine and caracurine II. J Chem Soc (B) 1971:691-695. Tröger base: Mason SF, Vane GW, Wells RJ, Whitehurst JS. Circular dichroism and absolute configuration of Tröger's base. J Chem Soc (B) 1967:553-556. Transstilbene oxide: Gottarelli G, Mason SF, Torre G. Circular dichroism and absolute configuration of (+)-trans-sfilbene oxide. J Chem Soc (B) 1970:1349-1353.
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23. b transition of the anthracene chromophore. In such a case the absolute configuration established by exciton analysis of the CD spectrum perfectly agrees with the one determined by X-ray analysis. [Harada N, Takuma Y, Uda H. The absolute stereochemistry of 6,15-dihydro-6,15-ethanonaphtho[2,3-c]-pentaphene and related homologues as determined by both exciton chirality and X-ray Bijvoet methods. J Am Chem Soc 1976;98: 5408-5409. Harada N, Takuma Y, Uda H. Synthesis and absolute stereochemistry of (+)-6,15-dihydro-6,15-ethanonaphtho[2,3-c]-pentaphene as determined by exciton chirality and X-ray Bijvoet methods. Bull Chem Soc Jpn 1977;50:2033-2038.] A second comment stated that the problem of the correct choice of the location of the electric transition moments on each of the coupled chromophores is related to the neglect of the chromophoric own magnetic dipole transition moments. In general (see Ref. 9a) the magnetic moments of the simple π→π* transitions are zero or small, so they can be neglected in an exciton calculation. An altemative approach to the solution of this problem has been proposed [Hezemans AMF, Groenewege MP. The absolute configuration and circular dichroism of (+)-(1,5)-diamino-triptycene. Tetrahedron 1973;29:1223-1226], who took full account of the magnetic moment of the low-energy aniline transition of (+)-1,5-diamino-trypticene, i.e., a molecule studied by Tanaka et al. [Tanaka J, Ogura F, Kuritani M, Nakagawa M. Circular dichroism and absolute configuration of 2,7-disubstituted triptycenes. Chimia 1972;26: 471-473] and showing the same problem presented by 1. With this nonapproximate treatment they obtained the correct configurational assignment, arriving in an independent way at the same conclusion of Mason (i.e., localization of the electric transition moments away from the amino group). This Referee pointed out that the Mason choice (velocity instead of length) does not necessarily correspond to a minimization of the magnetic dipole transition moment of the chromophore, so the correctness of his configurational assignment could be fortuitous. However, it is important to note that the velocity formalism only (Ref. 13) guarantees results which are independent of the choice of the origin, thus only they are physically meaningful. Finally, it must also be noticed that for the strongly allowed π-π* transitions of highly symmetric chromophores (benzene, naphthalene, etc.), the magnetic moment is zero, so these problems do not arise. Therefore, when the coupling of such strongly allowed transitions is used to assign the absolute configuration (as in the case of (6R, 15R)-(+)-6,15-dihydro-6,15-ethanonaphtho[2,3-c]-pentaphene above) a safe stereochemical conclusion is reached. It is interesting to note that the comments of the two Referees are not unrelated.
24. b transition of the anthracene chromophore. In such a case the absolute configuration established by exciton analysis of the CD spectrum perfectly agrees with the one determined by X-ray analysis. [Harada N, Takuma Y, Uda H. The absolute stereochemistry of 6,15-dihydro-6,15-ethanonaphtho[2,3-c]-pentaphene and related homologues as determined by both exciton chirality and X-ray Bijvoet methods. J Am Chem Soc 1976;98: 5408-5409. Harada N, Takuma Y, Uda H. Synthesis and absolute stereochemistry of (+)-6,15-dihydro-6,15-ethanonaphtho[2,3-c]-pentaphene as determined by exciton chirality and X-ray Bijvoet methods. Bull Chem Soc Jpn 1977;50:2033-2038.] A second comment stated that the problem of the correct choice of the location of the electric transition moments on each of the coupled chromophores is related to the neglect of the chromophoric own magnetic dipole transition moments. In general (see Ref. 9a) the magnetic moments of the simple π→π* transitions are zero or small, so they can be neglected in an exciton calculation. An altemative approach to the solution of this problem has been proposed [Hezemans AMF, Groenewege MP. The absolute configuration and circular dichroism of (+)-(1,5)-diamino-triptycene. Tetrahedron 1973;29:1223-1226], who took full account of the magnetic moment of the low-energy aniline transition of (+)-1,5-diamino-trypticene, i.e., a molecule studied by Tanaka et al. [Tanaka J, Ogura F, Kuritani M, Nakagawa M. Circular dichroism and absolute configuration of 2,7-disubstituted triptycenes. Chimia 1972;26: 471-473] and showing the same problem presented by 1. With this nonapproximate treatment they obtained the correct configurational assignment, arriving in an independent way at the same conclusion of Mason (i.e., localization of the electric transition moments away from the amino group). This Referee pointed out that the Mason choice (velocity instead of length) does not necessarily correspond to a minimization of the magnetic dipole transition moment of the chromophore, so the correctness of his configurational assignment could be fortuitous. However, it is important to note that the velocity formalism only (Ref. 13) guarantees results which are independent of the choice of the origin, thus only they are physically meaningful. Finally, it must also be noticed that for the strongly allowed π-π* transitions of highly symmetric chromophores (benzene, naphthalene, etc.), the magnetic moment is zero, so these problems do not arise. Therefore, when the coupling of such strongly allowed transitions is used to assign the absolute configuration (as in the case of (6R, 15R)-(+)-6,15-dihydro-6,15-ethanonaphtho[2,3-c]-pentaphene above) a safe stereochemical conclusion is reached. It is interesting to note that the comments of the two Referees are not unrelated.
25. b transition of the anthracene chromophore. In such a case the absolute configuration established by exciton analysis of the CD spectrum perfectly agrees with the one determined by X-ray analysis. [Harada N, Takuma Y, Uda H. The absolute stereochemistry of 6,15-dihydro-6,15-ethanonaphtho[2,3-c]-pentaphene and related homologues as determined by both exciton chirality and X-ray Bijvoet methods. J Am Chem Soc 1976;98: 5408-5409. Harada N, Takuma Y, Uda H. Synthesis and absolute stereochemistry of (+)-6,15-dihydro-6,15-ethanonaphtho[2,3-c]-pentaphene as determined by exciton chirality and X-ray Bijvoet methods. Bull Chem Soc Jpn 1977;50:2033-2038.] A second comment stated that the problem of the correct choice of the location of the electric transition moments on each of the coupled chromophores is related to the neglect of the chromophoric own magnetic dipole transition moments. In general (see Ref. 9a) the magnetic moments of the simple π→π* transitions are zero or small, so they can be neglected in an exciton calculation. An altemative approach to the solution of this problem has been proposed [Hezemans AMF, Groenewege MP. The absolute configuration and circular dichroism of (+)-(1,5)-diamino-triptycene. Tetrahedron 1973;29:1223-1226], who took full account of the magnetic moment of the low-energy aniline transition of (+)-1,5-diamino-trypticene, i.e., a molecule studied by Tanaka et al. [Tanaka J, Ogura F, Kuritani M, Nakagawa M. Circular dichroism and absolute configuration of 2,7-disubstituted triptycenes. Chimia 1972;26: 471-473] and showing the same problem presented by 1. With this nonapproximate treatment they obtained the correct configurational assignment, arriving in an independent way at the same conclusion of Mason (i.e., localization of the electric transition moments away from the amino group). This Referee pointed out that the Mason choice (velocity instead of length) does not necessarily correspond to a minimization of the magnetic dipole transition moment of the chromophore, so the correctness of his configurational assignment could be fortuitous. However, it is important to note that the velocity formalism only (Ref. 13) guarantees results which are independent of the choice of the origin, thus only they are physically meaningful. Finally, it must also be noticed that for the strongly allowed π-π* transitions of highly symmetric chromophores (benzene, naphthalene, etc.), the magnetic moment is zero, so these problems do not arise. Therefore, when the coupling of such strongly allowed transitions is used to assign the absolute configuration (as in the case of (6R, 15R)-(+)-6,15-dihydro-6,15-ethanonaphtho[2,3-c]-pentaphene above) a safe stereochemical conclusion is reached. It is interesting to note that the comments of the two Referees are not unrelated.
26. b transition of the anthracene chromophore. In such a case the absolute configuration established by exciton analysis of the CD spectrum perfectly agrees with the one determined by X-ray analysis. [Harada N, Takuma Y, Uda H. The absolute stereochemistry of 6,15-dihydro-6,15-ethanonaphtho[2,3-c]-pentaphene and related homologues as determined by both exciton chirality and X-ray Bijvoet methods. J Am Chem Soc 1976;98: 5408-5409. Harada N, Takuma Y, Uda H. Synthesis and absolute stereochemistry of (+)-6,15-dihydro-6,15-ethanonaphtho[2,3-c]-pentaphene as determined by exciton chirality and X-ray Bijvoet methods. Bull Chem Soc Jpn 1977;50:2033-2038.] A second comment stated that the problem of the correct choice of the location of the electric transition moments on each of the coupled chromophores is related to the neglect of the chromophoric own magnetic dipole transition moments. In general (see Ref. 9a) the magnetic moments of the simple π→π* transitions are zero or small, so they can be neglected in an exciton calculation. An altemative approach to the solution of this problem has been proposed [Hezemans AMF, Groenewege MP. The absolute configuration and circular dichroism of (+)-(1,5)-diamino-triptycene. Tetrahedron 1973;29:1223-1226], who took full account of the magnetic moment of the low-energy aniline transition of (+)-1,5-diamino-trypticene, i.e., a molecule studied by Tanaka et al. [Tanaka J, Ogura F, Kuritani M, Nakagawa M. Circular dichroism and absolute configuration of 2,7-disubstituted triptycenes. Chimia 1972;26: 471-473] and showing the same problem presented by 1. With this nonapproximate treatment they obtained the correct configurational assignment, arriving in an independent way at the same conclusion of Mason (i.e., localization of the electric transition moments away from the amino group). This Referee pointed out that the Mason choice (velocity instead of length) does not necessarily correspond to a minimization of the magnetic dipole transition moment of the chromophore, so the correctness of his configurational assignment could be fortuitous. However, it is important to note that the velocity formalism only (Ref. 13) guarantees results which are independent of the choice of the origin, thus only they are physically meaningful. Finally, it must also be noticed that for the strongly allowed π-π* transitions of highly symmetric chromophores (benzene, naphthalene, etc.), the magnetic moment is zero, so these problems do not arise. Therefore, when the coupling of such strongly allowed transitions is used to assign the absolute configuration (as in the case of (6R, 15R)-(+)-6,15-dihydro-6,15-ethanonaphtho[2,3-c]-pentaphene above) a safe stereochemical conclusion is reached. It is interesting to note that the comments of the two Referees are not unrelated.
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