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Total Synthesis of Mauritines A, B, C, and F: Cyclopeptide Alkaloids with a 14‐Membered Paracyclophane Unit
Author(s) -
Cristau Pierre,
TemalLaïb Taoues,
BoisChoussy Michèle,
Martin MarieThérèse,
Vors JeanPierre,
Zhu Jieping
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200401070
Subject(s) - chemistry , intramolecular force , stereochemistry , nucleophilic substitution , alcohol , nucleophile , nuclear magnetic resonance spectroscopy , peptide , medicinal chemistry , organic chemistry , catalysis , biochemistry
A unified strategy for the synthesis of mauritines A ( 5 ), B ( 6 ), C ( 7 ), and F ( 10 ) has been developed based on a key intramolecular nucleophilic aromatic substitution reaction (S N Ar) for the formation of the strained 14‐membered paracyclophane. It was demonstrated that the outcome of the cycloetherification is independent of the stereochemistry of the peptide backbone and that both (1 R )‐ 16 and (1 S )‐ 16 cyclized smoothly to provide the corresponding macrocycle. On the other hand, dehydration of the secondary benzylic alcohol, via the phenylselenide intermediate, is configuration dependent. (1 R )‐ 25 underwent the two‐step syn ‐elimination much more easily than (1 S )‐ 22 . A modified reductive deamination procedure via the diazonium intermediate was developed. A complete assignment of proton and carbon NMR spectroscopy signals for these natural products is reported for the first time.