Highly efficient asymmetric synthesis of fluvirucinine A1 via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA)-lipase-catalyzed acetylation tandem process.
ZACA-lipase-catalyzed acetylation tandem process has been shown to proceed satisfactorily with either TBS-protected 4-penten-1-ol or 3-buten-1-ol to provide the corresponding enantiomerically pure (R)-2-ethyl-1-alkanols. Either (R)-5 or (R)-6 was converted to 3 in seven steps. The other fragment 4 was synthesized in nine steps from (-)-(S)-citronellol. Conversion of 3 and 4 into 99% pure fluvirucinine A1 was achieved in four steps via amidation-ring closing metathesis, the overall yield in the longest linear sequence being 34% (13 steps).
Liang
Bo
B
Herbert C. Brown Laboratories of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907-2084, USA.
Negishi
Ei-ichi
E
D000107:Acetylation; D000080462:Acyclic Monoterpenes; D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003837:Deoxy Sugars / Q000737:chemistry; D007769:Lactams / Q000138:chemical synthesis* / Q000737:chemistry; D008049:Lipase / Q000378:metabolism*; D015394:Molecular Structure; D039821:Monoterpenes / Q000737:chemistry; D013237:Stereoisomerism; D015040:Zirconium / Q000737:chemistry*
D000080462:Acyclic Monoterpenes; D000475:Alkenes; D003837:Deoxy Sugars; D007769:Lactams; D039821:Monoterpenes; C526622:fluvirucinine A1; C070542:fluvirucin A1; D015040:Zirconium; D008049:Lipase; C007078:citronellol