title: A biomimetic total synthesis of (-)-spirotryprostatin B and related studies.
abstract: The prenylated natural products spirotryprostatin A and B derived from the Trp-Pro diketopiperazine also feature an oxidative rearrangement of the indole to form a spirooxindole. Synthetically, formation of the oxindole ring was stereoselectively accomplished by reaction of the appropriate indole precursor with N-bromosuccinimide. For optimum results, the oxidation should be carried out prior to diketopiperazine cyclization. In this manner, we have synthesized the tetrahydro- and dihydro- analogues of spirotryprostatin B in four steps from L-tryptophan methyl ester. The dihydro derivative was then converted to spirotryprostatin B by unsaturation of the pyrrolidine ring to a pyrroline, thus unambiguously confirming the structure of the natural product.
authors.affiliation: Institute of Molecular and Cell Biology, National University of Singapore.
authors.forename: H
authors.initials: H
authors.lastname: Wang
authors.forename: A
authors.initials: A
authors.lastname: Ganesan
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis / Q000737:chemistry / Q000494:pharmacology; D001232:Aspergillus fumigatus / Q000737:chemistry*; D002453:Cell Cycle / Q000187:drug effects; D003500:Cyclization; D010879:Piperazines / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D013141:Spiro Compounds / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D013237:Stereoisomerism; D013329:Structure-Activity Relationship; D014364:Tryptophan / Q000031:analogs & derivatives / Q000378:metabolism
chemical_list: D000470:Alkaloids; D010879:Piperazines; D013141:Spiro Compounds; C100698:demethoxyfumitremorgin C; C101781:spirotryprostatin B; C028129:tryptophan methyl ester; D014364:Tryptophan