Patai S., Rappoport Z. 1997 The chemistry of functional groups. The chemistry of double-bonded functional groups / 0155 260

OR2

H

The pure contribution from exciton coupling in testosterone 17ˇ-(p-chlorobenzoate) (152) was estimated by subtracting the CD spectra of exciton interaction-free 17ˇ-hydroxy- 4-en-3-one (153) and 4-en-3ˇ-ol-17ˇ-(p-chlorobenzoate) (154) from the experimental CD spectrum of 152. The exciton CD curve (C16.2 (247), 12.8 (230)) obtained is much more symmetrical, as required by the theory349. Several more examples of benzoates and sorbates of steroidal 4-en-3-ones were treated in similar way, thus smoothing the imbalance of the exciton Cotton effects due to contributions of component chromophores.

The absolute configuration of Wieland Miescher ketone analogues bearing an angular protected hydroxymethyl group was unambiguously determined after regioand stereoselective reduction of the saturated ketone function to cis-alcohols and application of the exciton chirality method to bicyclic enone-benzoate chromophoric systems 155 158352.

OH

R

4

O

(159)

R = CN +49.4 (261), −37.0 (227)

R = CO2 CH3 +50.5 (261), −38.9 (228)3 54

CHO

(CH3 )2 N

O

O

(160)

The (4R)-absolute configuration of a new chromophore of native visual pigment (159) (negative Cotton effect at 375 nm, negative Cotton effect at 254 nm) was established by the CD exciton chirality method applied to the 4-(dimethylamino)cinnamate (160). The split negative (381 nm) and positive (338 nm) exciton effects of 160 show a counterclockwise helicity between pentaenal and ˛-4-(dimethylamino)cinnamate chromophores355.

O

(162)

+5.10 (282), −7.97 (245)

Exciton interaction between p-methoxybenzoate and benzoyl chromophores in the preferred conformation of 161 allowed for assignment of the (˛R) absolute configuration on the basis of an observed negative exciton chirality356. This also correlates with the absolute configuration of a novel natural 4-methoxy-˛R,20 ,40-trihydroxydihydrochalcone. A series of 12 differently-substituted 161 or 162 analogues with an oxygenation pattern similar to that in natural flavonoids was reported by the same group. As with 161 or 162, exciton-type Cotton effects were observed288.

CH3 O

O

−9.9 (347), +8.2 (303), −15.8 (267)3 57

The absolute configuration of the benzocycloheptenone, ( )-isofavelol (163), was confirmed as (9R,12R) by X-ray crystallographic analysis of its 4-bromobenzoyl derivative, and by exciton chirality between the o-ketostyrene and 4-methoxybenzoate chromophores in 164357.

No exciton coupling was observed for the dialdehyde 165. The CD of (C)-166 also shows a simple pattern. The small amplitude of those Cotton effects can be attributed to the complicated polarization spectra of benzophenone chromophore and to the conformational flexibility of the 2-tolyl group. In contrast to (C)-165 and (C)-166, the quinone (C)-167 exhibits relatively strong Cotton effects ascribed to exciton interaction between favorably oriented transition moments in the 9,10-anthraquinone chromophore359.

The CD spectrum of ketone 168 also exhibits split Cotton effects: ε275 17.4 andε252 C24.7, corresponding to an intramolecular charge transfer transition at 261 nm (ε 28 300). Since this transition is polarized along the direction from the benzene ring to

O

H

O

HO

O

O

H

H

O

(169)

−37.6 (351), +22.9 (315), −12.6 (279),

−89.0 (254), +222.0 (217)3 6 1

250 Stefan E. Boiadjiev and David A. Lightner

the carbonyl group, a positive exciton chirality is predicted similar to other dibenz[a, h]anthracene derivatives where it was actually observed. It was suggested that homoconjugation between the two tetralone chromophores changes the relative sequence of relevant energy levels360.

The absolute configuration of diketone 169 was confirmed by comparison of the experimental CD with that calculated by the SCF-CI-Dipole Velocity MO method361.

By simplifying the chromophoric system of gilmaniellin 170 to m-divinylbenzene and applying the exciton chirality method to the CD couplet at 247 and 231 nm of 171, its absolute configuration was determined as shown362. The sign of n ! Ł CE (342 nm) is in agreement with the rule234, which correlates the CD of transoid enone (acetophenone moiety) with its helicity.

VII. ADDENDUM

The following references/data were found during a search of Chem. Abstr., Gen. Subject Index, ‘Circular dichroism’, Vol. 122 (Jan. June), 1995.

Conformational analysis of 3,3-disubstituted piperidin-4-ones (172) using NMR and CD spectroscopy was presented recently364.

Berg and Butkus365 reinvestigated the CD spectra of bicyclo[3.3.1]nonane-2,6-dione (69) and bicyclo[3.3.1]nonane-2,9-dione (70). They analyzed earlier reported CD spectral data159 and compared them with calculated CD using Schellman’s computational method. The comparison showed that the absolute configuration of ˛,ε-diketone ( )-69 is in agreement with the earlier assignment. The absolute configuration of the ( )-enantiomer of ˛, -diketone 70, however, has to be reversed to (1R,5S) as shown for 173. The incorrect earlier empirical assignment159 was explained by the spatial relationship of the two carbonyl chromophores in 173. In the major chair-boat conformer they are placed close to the nodal planes where Cotton effects change their sign. In addition, the cyclohexanedione ring in 173 adopts a boat conformation365. The calculations also confirmed strong transannular orbital interactions in 173, as was observed in 69366.

∆ε referred to one AMBE repeating unit 3 70 .

CD spectrum of (1R,3R,4R)-3-((1R,3R,4R)-1,7,7-trimethylbicyclo[2.2.1]-2-oxohept-3-yl)- 1,7,7-trimethylbicyclo[2.2.1]heptan-2-one (174, 3,30-dicamphor). This compound appears to be the first example of exciton coupling between two n ! Ł transitions from isolated carbonyl chromophores, as incorporated in ˛,υ-diketone 174.

VIII. ACKNOWLEDGMENTS

We wish to thank Professors Carl Djerassi, Albert Moscowitz and Gunther¨ Snatzke, without whose pioneering work much of what is written in this chapter would not have been possible. Special thanks go to those authors, Professors Djerassi and J. F. King, and journals or books for allowing use of illustrations from their articles.

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