Asymmetric Syntheses of the Macrocyclic Spermine Alkaloids (−)-(S)-Protoverbine, (−)-(S)-Buchnerine, and Their Naturally Occurring Congenial Alkaloids

✍ Scribed by Konstantin Drandarov; Armin Guggisberg; Manfred Hesse

• Publisher: John Wiley and Sons
• Year: 2002
• Tongue: German
• Weight: 205 KB
• Volume: 85
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/1522-2675(200204)85:4<979::aid-hlca979>3.0.co;2-f

✦ Synopsis

Dedicated to Prof. Hans-J¸rgen Hansen on the occasion of his 65th birthday Asymmetric syntheses of the following 17-membered macrocyclic spermine alkaloids are presented: (À)-(S)-protoverbine ( (8S)-8-phenyl-1,5,9,13-tetraazacycloheptadecane-6-one; 1), ()-(S)-protomethine ( (2S)-2-phenyl-1,5,9,14-tetraazabicyclo[12.3.1]octadecan-4-one; 2), (À)-(S)-buchnerine ( (8S)-8-(4-methoxyphenyl)-1,5,9,13-tetraazacycloheptadecane-6-one; 8), () 5,9,14-tetraazabicyclo[12.3.1]octadecan-4-one; 23), and ()-(S)-isoverbamekrine ( ()-(2S)-9-[(Z)-3-(4methoxyphenyl)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)-2acetoxy-2-phenylacetic acid are used as shift reagents for 1, 8, and related macrocyclic alkaloids are described.