- Isotope sensitive branching and kinetic isotope effects to analyse multiproduct terpenoid synthases from Zea mays
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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.
- Gatto, Nathalie,Vattekkatte, Abith,K?llner, Tobias,Degenhardt, J?rg,Gershenzon, Jonathan,Boland, Wilhelm
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supporting information
p. 3797 - 3800
(2015/03/30)
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- Asymmetric synthesis of highly enantiomerically enriched (S)(-)-β-bisabolene
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(S)-β-Bisabolene, (S)-1, was synthesized by a synthetic route in which (S)-4-methyl-3-cyclohexene carboxylic acid, (S)-10, which was the key intermediate, was prepared via a highly diastereoselective TiCl4-catalyzed Diels-Alder reaction between
- Argenti,Bellina,Carpita,Rossi
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p. 2909 - 2921
(2007/10/03)
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- CHIRAL LEAVING GROUP: ASYMMETRIC SYNTHESIS OF LIMONENE AND BISABOLENE
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The biogenetic-type asymmetric synthesis of limonene and bisabolenes is described.As model studies for the present asymmetric synthesis, the cyclization of catechol, biphenol and binaphthol mononeryl ethers 1, 4, and 5, with organoaluminium reagents are executed to furnish limonene as a major product.Since the reaction of 1, 4, and 5 has proved to proceed much faster than that of neryl phenyl ether under the similar conditions, the rate acceleration is attributed to the novel metal-anchimeric assistance of the aluminium reagents bound with the neighboring hydroxyl group for effecting the generation of the allyl cathion.This anchimeric effect is utilized for the enantioselective cyclization of (R)-(+)-1,1'-bi-2-naphthol mononeryl ether (8) upon treatment with modified aluminium reagent 9 to produce limonene with high optical purity (77percent ee).In a similar fashion, (R)-(+)-binaphtol (Z,Z)-monofarnesyl ether 16a undergoes the enantioselective cyclization to give β-bisabolene in 76percent ee.
- Sakane, Soichi,Fujiwara, Junya,Maruoka, Keiji,Yamamoto, Hisashi
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p. 2193 - 2202
(2007/10/02)
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