title: Substrate specificities of several prenyl chain elongating enzymes with respect to 4-methyl-4-pentenyl diphosphate.
abstract: In order to develop synthetic methods for biologically active homoallylic terpene sulfates, we examined the applicability and substrate specificities of several prenyl chain elongating enzymes with respect to 4-methyl-4-pentenyl diphosphate (homoIPP). The reaction of dimethylallyl diphosphate with homoIPP by use of Bacillus stearothermophilus (all-trans)-farnesyl diphosphate synthase resulted in efficient yields of cis-(yield: 45.9%) and trans-4,8-dimethylnona-3,7-dien-1-ol (homoGOH, 25.5%), which has a carbon skeleton of 4,8-dimethylnona-3-en-1-sulfate, an antiproliferative compound from a marine organism (Aiello, A. et al., Tetrahedron, 53, 11489-11492 (1997)). The homoIPP was found to be also active as a homoallylic substrate in place of isopentenyl diphosphate for Sulfolobus acidocaldarius geranylgeranyl diphosphate synthase to give diphosphate of cis- and trans-4,8,12-trimethyltrideca-3,7,11-trien-1-ol, for Micrococcus luteus B-P 26 hexaprenyl diphosphate synthase to give cis- and trans-4,8,12,16-tetramethylheptadeca-3,7,11,15-tetraen-1-ol (homoGGOH), and for Micrococcus luteus B-P 26 undecaprenyl diphosphate synthase to give cis-homoGGOH exclusively.
authors.affiliation: Department of Materials Science and Technology, Faculty of Science and Technology, Hirosaki University, Aomori 036-8561, Japan. nagaki@cc.hirosaki-u.ac.jp
authors.forename: Masahiko
authors.initials: M
authors.lastname: Nagaki
authors.forename: Yohei
authors.initials: Y
authors.lastname: Miki
authors.forename: Minori
authors.initials: M
authors.lastname: Nakada
authors.forename: Jun
authors.initials: J
authors.lastname: Kawakami
authors.forename: Haruo
authors.initials: H
authors.lastname: Kitahara
authors.forename: Yuji
authors.initials: Y
authors.lastname: Maki
authors.forename: Yoshinori
authors.initials: Y
authors.lastname: Gotoh
authors.forename: Tokuzo
authors.initials: T
authors.lastname: Nishino
authors.forename: Tanetoshi
authors.initials: T
authors.lastname: Koyama
mesh_terms: D019883:Alkyl and Aryl Transferases / Q000378:metabolism*; D006094:Gram-Positive Bacteria / Q000201:enzymology*; D045782:Hemiterpenes / Q000737:chemistry*; D010755:Organophosphates / Q000737:chemistry*; D013379:Substrate Specificity; D016945:Sulfolobus acidocaldarius / Q000201:enzymology*
chemical_list: C499975:4-methyl-4-pentenyl diphosphate; D045782:Hemiterpenes; D010755:Organophosphates; D019883:Alkyl and Aryl Transferases