Stereoselective epoxidation of bicyclic monoterpenes with tert-amyl hydroperoxide in presence of molybdenum compounds

Yur'ev, V. P.; Gailyunas, I. A.; Isaeva, Z. G.; Толстиков, Г. А.

doi:10.1007/bf00923530

Cited by 5 publications

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“…In another early example, the combination of tert-amyl hydroperoxide and either molybdenum hexacarbonyl or molybdenum pentachloride brought about specific and almost quantitative conversion of α-and β-pinenes or 2-or 3-carenes into their corresponding epoxides (Scheme 68) [91]. In closely related later work [92], the reaction of (+)-3-carene with the high oxidation state complex methyltrioxorhenium(VII), in the presence of a Lewis base, led to stereospecific, almost quantitative, formation of α-3,4-epoxycarene, 173α, along with the diol 174.…”

Section: Regiospecific Epoxidation Of Terpenesmentioning

confidence: 99%

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Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements

McGlinchey

2024

Molecules

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The impact of organometallic chemistry on the terpene field only really blossomed in the 1960s and 1970s with the realisation that carbon–carbon bond formation under mild conditions could be achieved by using nickel or iron carbonyls as synthetic reagents. Concomitantly, the development of palladium derivatives capable of the controlled coupling of isoprene units attracted the attention of numerous highly talented researchers, including future Nobel laureates. We discuss briefly how early work on the syntheses of simple monoterpenes soon progressed to sesquiterpenes and diterpenes of increasing complexity, such as humulene, flexibilene, vitamin A, or pheromones of commercial value, in particular those used in perfumery (muscone, lavandulol), or grandisol and red scale pheromone as replacements for harmful pesticides. As the field progressed, there has been more emphasis on developing organometallic routes to enantiopure rather than racemic products, as well as gaining precise mechanistic data on the transformations, notably the course of metal-promoted molecular rearrangements that have long been a feature of terpene chemistry. We note the impact of the enormously enhanced analytical techniques, high-field NMR spectroscopy and X-ray crystallography, and their use to re-examine the originally proposed structures of terpenes and their organometallic derivatives. Finally, we highlight the very recent ground-breaking use of the crystalline sponge method to acquire structural data on low-melting or volatile terpenes. The literature cited herein covers the period 1959 to 2023.

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Section: Regiospecific Epoxidation Of Terpenesmentioning

confidence: 99%

“…Scheme 67. Catalytic selective epoxidation of (left) geraniol and (right) linalool.In another early example, the combination of tert-amyl hydroperoxide and either molybdenum hexacarbonyl or molybdenum pentachloride brought about specific and almost quantitative conversion of αand β-pinenes or 2-or 3-carenes into their corresponding epoxides (Scheme 68)[91].…”

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confidence: 99%