Document Detail


meso-arylporpholactones and their reduction products.
MedLine Citation:
PMID:  22734444     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
The rational syntheses of meso-tetraaryl-3-oxo-2-oxaporphyrins 5, known as porpholactones, via MnO(4)(-)-mediated oxidations of the corresponding meso-tetraaryl-2,3-dihydroxychlorins (7) is detailed. Since chlorin 7 is prepared from the parent porphyrin 1, this amounts to a 2-step replacement of a pyrrole moiety in 1 by an oxazolone moiety. The stepwise reduction of the porpholactone 5 results in the formation of chlorin analogues, meso-tetraaryl-3-hydroxy-2-oxachlorin (11) and meso-tetraaryl-2-oxachlorins (12). The reactivity of 11 with respect to nucleophilic substitution by O-, N-, and S-nucleophiles is described. The profound photophysical consequences of the formal replacement of a pyrrole with an oxazolone (porphyrin-like chromophore) or (substituted) oxazole moiety (chlorin-like chromophore with, for the parent oxazolochlorin 12, red-shifted Q(x) band with enhanced oscillator strengths) are detailed and rationalized on the basis of SAC-CI and MNDO-PSDCI molecular orbital theory calculations. The single crystal X-ray structures of the porpholactones point at a minor steric interaction between the carbonyl oxygen and the flanking phenyl group. The essentially planar structures of all chromophores in all oxidation states prove that the observed optical properties originate from the intrinsic electronic properties of the chromophores and are not subject to conformational modulation.
Authors:
Christian Brückner; Junichi Ogikubo; Jason R McCarthy; Joshua Akhigbe; Michael A Hyland; Pedro Daddario; Jill L Worlinsky; Matthias Zeller; James T Engle; Christopher J Ziegler; Matthew J Ranaghan; Megan N Sandberg; Robert R Birge
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Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, Non-P.H.S.     Date:  2012-07-19
Journal Detail:
Title:  The Journal of organic chemistry     Volume:  77     ISSN:  1520-6904     ISO Abbreviation:  J. Org. Chem.     Publication Date:  2012 Aug 
Date Detail:
Created Date:  2012-08-03     Completed Date:  2012-12-11     Revised Date:  2013-08-13    
Medline Journal Info:
Nlm Unique ID:  2985193R     Medline TA:  J Org Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  6480-94     Citation Subset:  IM    
Affiliation:
Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060, USA. c.bruckner@uconn.edu
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MeSH Terms
Descriptor/Qualifier:
Crystallography, X-Ray
Lactones / chemical synthesis*,  chemistry
Models, Molecular
Molecular Structure
Oxidation-Reduction
Grant Support
ID/Acronym/Agency:
GM-34548/GM/NIGMS NIH HHS; R01 GM034548/GM/NIGMS NIH HHS
Chemical
Reg. No./Substance:
0/Lactones
Comments/Corrections

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