Progress in Optical Circular Dichroism

Velluz, L; Legrand, M.

doi:10.1002/anie.196508381

Cited by 99 publications

(16 citation statements)

References 17 publications

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“…Assuming a similar preferred conformation for the salicylidenimino group about its attachment bond and this sector rule, the sign of the Cotton effect near 315 nm shown by the N-salicylidenes of a number of 20-aminopregnanes can be predicted (6,7). Much the same is true for the N-salicylidenes of cyclic amines, especially 17u-, 17P-, and 3u-amino steroids (8).…”

Section: D) Curves Of the N-salicylidenes [(S)-lb And (S)-2b] Of (S)mentioning

confidence: 94%

Optically Active Amines. Part XIII. Circular Dichroism of the N-Salicylidene Derivatives of Alkylamines

Smith¹,

Ensley²

1971

Can. J. Chem.

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Comparison of the c.d. spectra of (3-(+)-N-salicylidene-a-phenylethylamine with those of (3-(+)-Nsalicylidene-sec-butylamine and (R)-(-)-N-salicylidene-2,2-dimethyl-3-aminobutane confirms the conclusion that the strong rotational strength shown by N-salicylidene-a-and P-phenylalkylamines is due to an interaction of the n-electron system of the phenyl group and the salicylidenimino chromophore. The sign of the Cotton effects near 255 and 315 nm shown by the N-salicylidenes of alkylamines and cycloalkylamines, when these are conformationally defined, can be correlated with their absolute configurations using a planar sector rule, similar to that used fo'c the interpretation of the c.d. and 0.r.d. spectra of N-salicylidene-a-and !3-phenylalkylamines.La comparaison des spectres de d.c. du S-(+)-N-salicylidene a-phknylethylamine avec ceux du S-(+)-N-salicylidene sec-butylamine et R-(-)-N-salicylidene dimethyl-2,2 amino-3 butane confirme le fait que I'importance de la force de rotation qui se manifeste dans les N-salicylidtne a et 13-phCnylalkylamines, est due a une interaction des electrons n du groupe phenyle avec le chromophore salicylidenimino. Les signes des effets Cotton entre 255 et 315 nm dans les N-salicylidenes d'alkylamines, dans une conformation definie, peuvent Etre relies aux configurations absolues en utilisant le mtme genre de regle que celle utilisee dans I'interpretation des spectres de d.c. et d.0.r. des N-salicylidtne a et a-phenylalkylamines.

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Section: D) Curves Of the N-salicylidenes [(S)-lb And (S)-2b] Of (S)mentioning

confidence: 94%

Optically Active Amines. Part XIII. Circular Dichroism of the N-Salicylidene Derivatives of Alkylamines

Smith¹,

Ensley²

1971

Can. J. Chem.

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“…This is because the chirality is intrinsic to the molecules and not a function of their orientation in space. For surveys of this subject the y-eader is referred to the monographs by Crabb~ (1972) and by Velluz, Legrand and Grosjean (1965). The applications to photosynthesis have.…”

Section: Circular Dichroismmentioning

confidence: 99%

Primary Events and the Trapping of Energy

Sauer¹

1975

Energetics of Photosynthesis

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“…Circular dichroism spectra were taken on JASCO J5 and J20 spectrophotometers calibrated for wavelength and dichroic absorption with 5n-cholestan-3-one in I ,4-dioxan (AE + 1.13 at 295 nm (20)). Low temperature measurements (21) were corrected for volume contraction from published solvent data (22).…”

Section: Methodsmentioning

confidence: 99%

“…Band I was even more sensitive to changes in temperature and solvent polarity for [19][20][21][22][23][24][25] (Table 3). There was no clear correlation of the molecular ellipticity of band I with the usual solvent parameters (33), and, as noted above, it increased linearly in magnitude with decreasing temperature.…”

Section: Alk~~ibic~cloj221ii7~~~~t~~i Nitrcitc~ (12-18)mentioning

confidence: 99%

Circular Dichroism of Nitrate Esters: A Planar Symmetry Rule for the Nitrato Chromophore

Barton¹,

Hayward²

1972

Can. J. Chem.

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Conformational analysis of nitrate esters based on X-ray and spectroscopic data showed the nitrato group to be coplanar with the a carbon atom and, in the preferred rotamer, the nitro moiety to be antiperiplanar to the /I carbon atom. Three optically active absorption bands not apparent in the isotropicelectronic spectra were resolved in the circular dichroism spectra. Band I (270 nm) reflected nitrato group libration changing sign and magnitude with changes in temperature and solvent polarity. Differences in rotatory strength of band 111 (210 nm) for cis-and trans-dinitrates indicated transition moment coupling. A planar symmetry rule for chromophores in the C, point group correlated the molecular geometry and sign of band I1 for 42 nitrate esters: when the lowest-energy rotamer of the nitrate ester is viewed down the 0-C bond with the nitro group uppermost rotatory contributions to band I1 (230 nm) are positive for perturbing atoms to the right and negative for those to the left of the nitrato symmetry plane.L'analyse conformationnelle des esters nitriques, baste sur les donntes de la spectroscopie et des rayons-)<, montre que le groupe nitrate est coplanaire avec I'atome de carbone en a et que, dans le rotamere priviltgit, le fragment nitro est antiptriplanaire a I'atome de carbone en /I. Trois bandes d'absorption optiquement actives, non apparentes sur le spectre tlectronique isotrope, ont t t t rtsolues dans le spectre de dichroisme circulaire. La bande I (270 nm) reflete la vibration du groupe nitro et change de signe et d'amplitude lorsque la temptrature et la polaritt du solvant changent. Les differences dans le pouvoir rotatoire de la bande I11 (2i0 nm) pour les dinitrates ci.s et trat1.s indiquent un couplage du moment de transition. Une rtgle de symttrie plane pour les chromophores du groupe C, relie la gtomttrie moltculaire au signe de la bande 11 pour 42 esters nitriques: lorsque le rotamtre de plus basse energie de I'ester nitrique est regard6 le long de la liaison 0-C avec le groupe nitro, les contributions rotatoires decisives pour la bande I1 (230 nm) sont positives lorsque les atomes sont situes a droite du plan de symttrie du nitrate et negatives lorsqu'ils sont a gauche.

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Progress in Optical Circular Dichroism

Cited by 99 publications

References 17 publications

Optically Active Amines. Part XIII. Circular Dichroism of the N-Salicylidene Derivatives of Alkylamines

Optically Active Amines. Part XIII. Circular Dichroism of the N-Salicylidene Derivatives of Alkylamines

Primary Events and the Trapping of Energy

Circular Dichroism of Nitrate Esters: A Planar Symmetry Rule for the Nitrato Chromophore

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