Synthesis of (+)-didemniserinolipid B: application of a 2-allyl-4-fluorophenyl auxiliary for relay ring-closing metathesis.
The synthesis of didemniserinolipid B utilizing a ketalization/ring-closing metathesis (K/RCM) strategy is described. In the course of this work, a novel 2-allyl-4-fluorophenyl auxiliary for relay ring-closing metathesis (RRCM) was developed, which increased the yield of the RCM. The resulting 6,8-dioxabicyclo[3.2.1]octene core was selectively functionalized by complimentary dihydroxylation and epoxidation routes to install the C10 axial alcohol. This bicyclic ketal core was further functionalized by etherification and an alkene cross metathesis with an unsaturated alpha-phenylselenyl ester en route to completing the total synthesis.
Marvin
Christopher C
CC
Department of Chemistry, University of Wisconsin-Madison,1101 University Avenue, Madison, Wisconsin 53706-1322, USA.
Voight
Eric A
EA
Suh
Judy M
JM
Paradise
Christopher L
CL
Burke
Steven D
SD
D000475:Alkenes; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis*; D003500:Cyclization; D009795:Octanes / Q000737:chemistry*; D011409:Propylene Glycols / Q000138:chemical synthesis*
D000475:Alkenes; D001643:Bridged Bicyclo Compounds; D009795:Octanes; D011409:Propylene Glycols; C467921:didemniserinolipid B