A new stereocontrolled total synthesis of the mast cell inhibitory alkaloid, (+)-monanchorin, via the Wittig reaction of a stabilized ylide with a cyclic guanidine hemiaminal.
An asymmetric total synthesis of the mast cell inhibitor (+)-monanchorin is reported in which a Sharpless AD on 11 and a cyclic sulfate ring opening with an azide feature as key steps. After further manipulation, a novel guanidine-controlled ester reduction provided the guanidine-hemiaminal 25 which underwent Wittig olefination to give 27. Hydrogenation and a second guanidine-controlled reduction of the ester in 28, to obtain aldehyde 29, then set up a trifluoroacetic acid mediated cyclization to give (+)-monanchorin TFA salt.
The School of Chemistry and Chemical Engineering and the Centre for Cancer Research and Cell Biology (CCRCB), Queen's University Belfast (QUB) , Stranmillis Road, Belfast BT95 AJ, Northern Ireland, United Kingdom.
Karl J
KJ
Hale
Liping
L
Wang
D000447:Aldehydes / Q000138:chemical synthesis / Q000737:chemistry; D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology*; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology*; D003500:Cyclization; D004952:Esters; D019791:Guanidine / Q000737:chemistry*; D006146:Guanidines / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology*; D008407:Mast Cells / Q000187:drug effects*; D015394:Molecular Structure; D013237:Stereoisomerism
D000447:Aldehydes; D000470:Alkaloids; D019086:Bridged Bicyclo Compounds, Heterocyclic; D004952:Esters; D006146:Guanidines; C488575:monanchorin; D019791:Guanidine