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Asymmetric Syntheses of the Macrocyclic Spermine Alkaloids (−)‐( S )‐Protoverbine, (−)‐( S )‐Buchnerine, and Their Naturally Occurring Congenial Alkaloids
Author(s) -
Drandarov Konstantin,
Guggisberg Armin,
Hesse Manfred
Publication year - 2002
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 - 10.1002/1522-2675(200204)85:4<979::aid-hlca979>3.0.co;2-f
Subject(s) - chemistry , stereochemistry , phenylacetic acid , enantiomer , spermine , organic chemistry , enzyme
Asymmetric syntheses of the following 17‐membered macrocyclic spermine alkaloids are presented: (−)‐( S )‐protoverbine (=(8 S )‐8‐phenyl‐1,5,9,13‐tetraazacycloheptadecane‐6‐one; 1 ), (+)‐( S )‐protomethine (=(2 S )‐2‐phenyl‐1,5,9,14‐tetraazabicyclo[12.3.1]octadecan‐4‐one; 2 ), (−)‐( S )‐buchnerine (=(8 S )‐8‐(4‐methoxyphenyl)‐1,5,9,13‐tetraazacycloheptadecane‐6‐one; 8 ), (+)‐( S )‐verbamethine (=(+)‐(2 S )‐9‐[( E )‐phenylprop‐2‐enoyl]‐2‐phenyl‐1,5,9,14‐tetraazabicyclo[12.3.1]octadecan‐4‐one; 4 ), (−)‐( S )‐verbacine (=(−)‐(8 S )‐1‐[( E )‐phenylprop‐2‐enoyl]‐8‐phenyl‐1,5,9,13‐tetraazacycloheptadecan‐6‐one; 3 ), (−)‐( S )‐verbasikrine (=(−)‐(8 S )‐1‐[( E )‐3‐(4‐methoxyphenyl)prop‐2‐enoyl]‐8‐phenyl‐1,5,9,13‐tetraazacycloheptadecan‐6‐one; 26 ), (−)‐( S )‐isoverbasikrine (=(−)‐(8 S )‐1‐[( Z )‐3‐(4‐methoxyphenyl)prop‐2‐enoyl]‐8‐phenyl‐1,5,9,13‐tetraazacycloheptadecan‐6‐one; 25 ), (+)‐( S )‐verbamekrine (=(+)‐(2 S )‐9‐[( E )‐3‐(4‐methoxyphenyl)prop‐2‐enoyl]‐2‐phenyl‐1,5,9,14‐tetraazabicyclo[12.3.1]octadecan‐4‐one; 23 ), and (+)‐( S )‐isoverbamekrine (=(+)‐(2 S )‐9‐[( Z )‐3‐(4‐methoxyphenyl)prop‐2‐enoyl]‐2‐phenyl‐1,5,9,14‐tetraazabicyclo[12.3.1]octadecan‐4‐one; 24 ). Effective methods for 1 H‐NMR determination of the enantiomeric purity in which ( S )‐2‐hydroxy‐2‐phenylacetic acid and ( S )‐2‐acetoxy‐2‐phenylacetic acid are used as shift reagents for 1, 8 , and related macrocyclic alkaloids are described.