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D 2 ‐Symmetric Chiroporphyrins Derived from (1 R )‐ cis ‐Hemicaronaldehydic Acid: Preparation and Spectral Characterization
Author(s) -
Pérollier Céline,
Mazzanti Marinella,
Simonato JeanPierre,
Launay Franck,
Ramasseul René,
Marchon JeanClaude
Publication year - 2000
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(200002)2000:4<583::aid-ejoc583>3.0.co;2-e
Subject(s) - chemistry , stereocenter , enantiopure drug , amide , atropisomer , synthon , ligand (biochemistry) , yield (engineering) , catalysis , proton nmr , pyrrole , stereochemistry , porphyrin , enantioselective synthesis , medicinal chemistry , organic chemistry , materials science , biochemistry , receptor , metallurgy
Esters, N , N ‐disubstituted amides, and a N ‐acylurea derived from the enantiopure industrial intermediate (1 R )‐ cis ‐hemicaronaldehydic acid (or biocartol) are convenient synthons for the preparation of a series of chiroporphyrins by condensation with pyrrole. These chiral meso ‐tetracyclopropylporphyrins are obtained exclusively as the D 2 ‐symmetric α,β,α,β atropisomer, generally in low to moderate yields (2‐20%), and in the urea case in excellent yield (60%). Hydrolysis of the urea substituents affords a chiroporphyrin with mono‐ N ‐substituted amide groups. 1 H‐NMR spectroscopy indicates that the ester, amide, and urea stereogenic groups sit on the porphyrin close to the metal binding site and restrict substrate or ligand access along a C 2 ‐symmetric groove. This structural feature of chiroporphyrins and of their metal complexes is of high potential interest in asymmetric catalysis and chiral recognition.