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The Macrocyclic Spermidine Alkaloid (−)‐( S )‐Neoperiphylline: Revision of the Structure Based on the Total Synthesis
Author(s) -
Sergeyev Sergey A.,
Hesse Manfred
Publication year - 2003
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200390046
Subject(s) - chemistry , alkaloid , total synthesis , isomerization , natural product , stereochemistry , spermidine , organic chemistry , enzyme , catalysis
The total synthesis of the two isomeric macrocyclic enamides 2 and 17 is described. The precursor 14 was synthesized by means of template‐assisted macrocyclization ( Scheme 2 ). Isomerization of 14 in the presence of [Fe(CO) 5 ] gave 2 and 17 ( Scheme 4 ). Structure 2 was previously assigned to the alkaloid neoperiphylline. However, the synthetic 2 showed completely different properties compared to the earlier described data of the natural compound. Surprisingly, analytical data of the second synthetic product 17 were very close to those of the natural neoperiphylline. We conclude that the previously assigned structure of neoperiphylline is erroneous and should be corrected to that of (−)‐(4 S ,12 Z )‐4‐phenyl‐9‐[(2 E )‐3‐phenylprop‐2‐enoyl]‐1,5,9‐triazacyclotridec‐12‐en‐2‐one ( 17 ).