title: Stepwise cyclopropanation on the polycyclopropanated polyketide formation in jawsamycin biosynthesis.
abstract: Jawsamycin is a polyketide-nucleoside hybrid with a unique polycyclopropane moiety on a single polyketide chain. The unexpected isolation of cyclopropane deficient jawsamycin analogs allowed us to propose a stepwise cyclopropanation mechanism for the enzymatic synthesis of this polyketide. The concise timing of the cyclopropanation could be regulated by a delicate balance between reaction rates of the condensation and cyclopropanation reactions.
authors.affiliation: Division of chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan. hoik@sci.hokudai.ac.jp.
authors.forename: Tomoshige
authors.initials: T
authors.lastname: Hiratsuka
authors.affiliation: Division of chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan. hoik@sci.hokudai.ac.jp.
authors.forename: Hideaki
authors.initials: H
authors.lastname: Suzuki
authors.affiliation: Division of chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan. hoik@sci.hokudai.ac.jp.
authors.forename: Atsushi
authors.initials: A
authors.lastname: Minami
authors.affiliation: Division of chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan. hoik@sci.hokudai.ac.jp.
authors.forename: Hideaki
authors.identifier: http://orcid.org/0000-0002-6947-3397
authors.initials: H
authors.lastname: Oikawa
mesh_terms: D001688:Biological Products / Q000737:chemistry / Q000378:metabolism*; D003521:Cyclopropanes / Q000737:chemistry / Q000378:metabolism*; D015394:Molecular Structure; D061065:Polyketides / Q000737:chemistry / Q000378:metabolism*; D011108:Polymers / Q000737:chemistry / Q000378:metabolism*
chemical_list: D001688:Biological Products; D003521:Cyclopropanes; D061065:Polyketides; D011108:Polymers; C000626489:jawsamycin