Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements
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...
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| Format: | Article |
| Language: | English |
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MDPI AG
2024-03-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/29/6/1409 |
| _version_ | 1797239855473754112 |
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| author | Michael J. McGlinchey |
| author_facet | Michael J. McGlinchey |
| author_sort | Michael J. McGlinchey |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-04-24T17:58:10Z |
| format | Article |
| id | doaj.art-483c50def5f54988a6bdf4ce3a829200 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-04-24T17:58:10Z |
| publishDate | 2024-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-483c50def5f54988a6bdf4ce3a8292002024-03-27T13:57:18ZengMDPI AGMolecules1420-30492024-03-01296140910.3390/molecules29061409Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular RearrangementsMichael J. McGlinchey0School of Chemistry, University College Dublin, Belfield, D04 V1W8 Dublin, IrelandThe 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.https://www.mdpi.com/1420-3049/29/6/1409nickel and iron carbonylsallyl-palladium couplingspheromonesring-strained terpenesMcMurry couplingepoxidations |
| spellingShingle | Michael J. McGlinchey Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements Molecules nickel and iron carbonyls allyl-palladium couplings pheromones ring-strained terpenes McMurry coupling epoxidations |
| title | Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements |
| title_full | Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements |
| title_fullStr | Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements |
| title_full_unstemmed | Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements |
| title_short | Organotransition Metal Chemistry of Terpenes: Syntheses, Structures, Reactivity and Molecular Rearrangements |
| title_sort | organotransition metal chemistry of terpenes syntheses structures reactivity and molecular rearrangements |
| topic | nickel and iron carbonyls allyl-palladium couplings pheromones ring-strained terpenes McMurry coupling epoxidations |
| url | https://www.mdpi.com/1420-3049/29/6/1409 |
| work_keys_str_mv | AT michaeljmcglinchey organotransitionmetalchemistryofterpenessynthesesstructuresreactivityandmolecularrearrangements |