Diene chirality and cotton effects of nonhomoannular cisoid conjugated dienes: Circular dichroism and crystal structure of a steroidal 19-nor-1(10),9(11)-diene derived from westphalen's diol diacetate

Nonhomoannular cisoid conjugated dienes exhibit negative lowest‐energy π→π* Cotton effects when they have P diene chirality and positive CEs when they have M diene chirality. We investigated this relationship further with a variety of such dienes by MM2 conformational energy‐minimization calculation...

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Published in:Chirality (New York, N.Y.) N.Y.), 2002, Vol.14 (2-3), p.180-186
Main Authors: Burgstahler, Albert W., Jahansouz, Hossain, Véliz, Eduardo A., Takasugawa, Fusao
Format: Article
Language:English
Subjects:
allylic/homoallylic chirality contributions
CH/π interactions
Cotton effects
diene chirality
MM2 force-field conformational minimizations
steroid and terpenoid nonhomoannular dienes
Westphalen's diol
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Summary:Nonhomoannular cisoid conjugated dienes exhibit negative lowest‐energy π→π* Cotton effects when they have P diene chirality and positive CEs when they have M diene chirality. We investigated this relationship further with a variety of such dienes by MM2 conformational energy‐minimization calculations and by an X‐ray crystal structure of a steroidal 19‐nor‐1(10),9(11)‐diene. CEs are stronger when each double bond of the diene is endocyclic in a different ring and weaker when only one of the double bonds is endocyclic or when neither double bond is endocyclic. They are also stronger when axial allylic and homoallylic substituents with CH/π interactions are present that exert consignate chirality contributions. Chirality 14:180–186, 2002. © 2002 Wiley‐Liss, Inc.
ISSN:0899-0042
1520-636X
DOI:10.1002/chir.10067