142-50-7Relevant articles and documents
Stereochemical investigations on the biosynthesis of achiral (Z)-γ-bisabolene in Cryptosporangium arvum
Rinkel, Jan,Dickschat, Jeroen S.
supporting information, p. 789 - 794 (2019/04/17)
A newly identified bacterial (Z)-γ-bisabolene synthase was used for investigating the cyclisation mechanism of the sesquiterpene. Since the stereoinformation of both chiral putative intermediates, nerolidyl diphosphate (NPP) and the bisabolyl cation, is lost during formation of the achiral product, the intriguing question of their absolute configurations was addressed by incubating both enantiomers of NPP with the recombinant enzyme, which resolved in an exclusive cyclisation of (R)-NPP, while (S)-NPP that is non-natural to the (Z)-γ-bisabolene synthase was specifically converted into (E)-β-farnesene. A hypothetical enzyme mechanistic model that explains these observations is presented.
Isotope sensitive branching and kinetic isotope effects to analyse multiproduct terpenoid synthases from Zea mays
Gatto, Nathalie,Vattekkatte, Abith,K?llner, Tobias,Degenhardt, J?rg,Gershenzon, Jonathan,Boland, Wilhelm
supporting information, p. 3797 - 3800 (2015/03/30)
Multiproduct terpene synthases TPS4-B73 and TPS5-Delprim from Zea mays exhibit isotopically sensitive branching in the formation of mono- and sesquiterpene volatiles. The impact of the kinetic isotope effects and the stabilization of the reactive intermediates by hyperconjugation along with the shift of products from alkenes to alcohols are discussed.
Biomimetic total synthesis of (-)-neroplofurol and (+)-ekeberin D4triggered by hydrolysis of terminal epoxides
Kodama, Takeshi,Aoki, Shingo,Matsuo, Tomoki,Tachi, Yoshimitsu,Nishikawa, Keisuke,Morimoto, Yoshiki
supporting information, p. 1662 - 1664 (2015/02/19)
To accumulate the chemi cal basis of epoxide-opening cascade biogenesis, chemical syntheses of sesqui- and triterpenoids were performed. The biomi metic total syntheses of (-)-neroplofurol (1) and (+)-ekeberin D4(2) were accomplished by protic acid-catalyzed hydrolysis of the terminal epoxide from nerolidol diepoxide 3 and squalene tetraepoxide 4 through single and double 5-exo cyclizations in intermediates 5 and 6, respectively. This chemical reaction mimics the direct hydrolysis mechanism of epoxide hydrol ases, enzymes that catalyze an epoxide-opening reaction to finally produce vicinal diols.
Biosynthesis of the sesquiterpene botrydial in Botrytis cinerea. Mechanism and stereochemistry of the enzymatic formation of presilphiperfolan-8β-ol
Wang, Chieh-Mei,Hopson, Russell,Lin, Xin,Cane, David E.
supporting information; experimental part, p. 8360 - 8361 (2009/10/24)
(Figure Presented) Presilphiperfolan-8β-ol synthase, encoded by theBcBOT2 gene from the necrotrophic plant pathogen Botrytis cinerea, cata lyzes the multistep cyclization of farnesyl diphosphate (2) to the tricyclic sesquiterpene alcohol presilphiperfolan-8β-ol (3), the preursor of the phytotoxin botrydial, a strain-dependent fungal virulence factor. Incubation of (1R)-[1-2H]farnesyl diphosphate (2b) with recombinant presilphiperfolan-8β-ol synthase gave exclusively (5R)-[5α-2H]-3b, while complementary incubation of (1S)-[1-2H]FPP (2c) gave (5S)-[5β-2H]-3c. These results establishedthat cyclization of farnesyl diphosphate involves displacement of the d iphosphate group from C-1 with net inversion of configuration and ruled out the proposed intermediacy of the cisoid conformer of nerolidyl diphosphate (9) in the cyclization. While not a mandatory intermediate, (3R)-nerolidyl diphosphate was shown to act as a substrate surrogate. Cyclization of [13,13,13-2H3] farnesyl diphosphate (2d) gave [14,14,14-2H3]-3d, thereby establishing that electrophilic attack takes place exclusively on the si face of the 12,13-double bond of 2. The combined results provide a detailed picture of theconformation of enzyme-bound farnesyl diphosphate at the active site of presilphiperfolan-8β-ol synthase.
The synthesis of (3R)-nerolidol
Cane, David E.,Ha, Hyun-Joon,McIlwaine, Douglas B.,Pascoe, Keith O.
, p. 7553 - 7554 (2007/10/02)
The sesquiterpene natural product (3R)-nerolidol has been prepared in six steps starting from (3R)linalool.
(10R, 11R)-(+)-SQUALENE-10, 11-EPOXIDE: ISOLATION FROM LAURENCIA OKAMURAI AND THE ASYMMETRIC SYNTHESIS
Kigoshi, Hideo,Ojika, Makoto,Shizuri, Yoshikazu,Niwa, Haruki,Yamada, Kiyoyuki
, p. 5413 - 5414 (2007/10/02)
From a red alga Laurencia okamurai, (10R, 11R)-(+)-squalene-10, 11-epoxide 1 was isolated and its asymmetric synthesis has been achieved starting from trans, trans-farnesol.
