Quasiracemic synthesis: concepts and implementation with a fluorous tagging strategy to make both enantiomers of pyridovericin and mappicine.
The concept of quasiracemic synthesis is introduced and illustrated with syntheses of both enantiomers of pyridovericin (whose absolute configuration is assigned as R) and mappicine. Like racemic synthesis, quasiracemic synthesis provides both enantiomers in a single synthetic sequence; however, separation tagging is used to ensure that quasiracemic mixtures can be analyzed, separated, and identified on demand. Fluorous tags of differing chain lengths are used to tag two enantiomeric starting materials. The resulting quasienantiomers are mixed to make a quasiracemate, which is then treated like a true racemate in successive steps of the synthesis. Fluorous chromatography is used to separate, or demix, the final quasiracemate into its two components, which are then detagged to provide (true) enantiomeric products. Quasiracemic synthesis is portrayed as the first and simplest of a series of mixture synthesis techniques based on separation tagging, and the prospects for using other types of separation tags are briefly evaluated.
Zhang
Qisheng
Q
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
Rivkin
Alexey
A
Curran
Dennis P
DP
D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D000900:Anti-Bacterial Agents / Q000138:chemical synthesis* / Q000737:chemistry; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D019906:Nuclear Magnetic Resonance, Biomolecular / Q000379:methods; D011728:Pyridones / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D000470:Alkaloids; D000900:Anti-Bacterial Agents; D006845:Hydrocarbons, Fluorinated; D011728:Pyridones; C114116:pyridovericin; C008325:mappicine