Preparation and characterization of cyclopalladated complexes derived from l-(−)-fenchone

Dickmu, Gerard C.; Smoliakova, Irina P.

doi:10.1016/j.jorganchem.2014.08.022

Cited by 9 publications

(2 citation statements)

References 60 publications

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“…In recent years, the discovery and application of new chiral auxiliaries and catalysts have become a crucial question in stereoselective syntheses [ 1 , 2 , 3 , 4 ]. To achieve new, efficient, and commercially available chiral catalysts, natural chiral terpenes [ 5 ], including (+)-pulegone [ 6 , 7 , 8 ], α- and β-pinene [ 9 , 10 , 11 , 12 , 13 , 14 ], and fenchone-camphor [ 15 , 16 , 17 , 18 , 19 ] have proved to be excellent sources. Starting from these readily available natural sources, several powerful chiral catalysts, including various di- and trifunctional synthons, such as 1,3-aminoalcohols and aminodiols, have been applied in stereoselective syntheses [ 5 , 20 ].…”

Section: Introductionmentioning

confidence: 99%

Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol

et al. 2018

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A library of bidentate diols, as well as tridentate triols and aminodiols, derived from (+)-sabinol, was synthesized in a stereoselective manner. Sabinol was transformed into allylic trichloroacetamide via Overman rearrangement of the corresponding trichloroacetimidate. After changing the protecting group to Boc, the enamine was subjected to stereospecific dihydroxylation with OsO4/NMO, resulting in the (1R,2R,3R,5R)-aminodiol diastereomer. The obtained primary aminodiol was transformed to a secondary analogue. The ring closure of the N-benzyl-substituted aminodiol with formaldehyde was investigated and regioselective formation of the spiro-oxazolidine ring was observed. Hydroboration or dihydroxylation of sabinol or its benzyl ether with OsO4/NMO resulted in the formation of sabinane-based diols and triols following a highly stereospecific reaction. Treatment of sabinol with m-CPBA afforded O-benzoyl triol as a diastereoisomer of the directly dihydroxylated product, instead of the expected epoxy alcohol. The resulting aminodiols, diol, and triols were applied as chiral catalysts in the reaction of diethylzinc and benzaldehyde from moderate to good selectivity.

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Section: Introductionmentioning

confidence: 99%

Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol

et al. 2018

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“…As noted in the introduction, chiral terpenoids have long been incorporated into coordination compounds as part of the search for improved catalysts in asymmetric syntheses, and these have since been modified to possess a metal carbon σ-bond, thereby linking the metal directly to the asymmetric moiety. Typically, readily available and inexpensive (1 R )-(-)-fenchone is convertible into an imine that, when cyclopalladated, yields systems such as 221 that can easily be further elaborated ( Scheme 87 ) [ 120 ]. A different application of this approach involves the reaction of (C 5 Me 5 )Co(PPh 3 ) 2 with β-pinene, whereupon bond fission leads to 222 containing both η 1 - and η 3 -allyl attachments to cobalt, a structure closely analogous to that of the iron complex 161 shown in Figure 4 .…”

Section: Discussionmentioning

confidence: 99%

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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Cyclopalladated complexes containing an (sp3)C–Pd bond

Dickmu

Smoliakova

2020

Coordination Chemistry Reviews

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Preparation and characterization of cyclopalladated complexes derived from l-(−)-fenchone

Cited by 9 publications

References 60 publications

Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol

Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol

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

Cyclopalladated complexes containing an (sp3)C–Pd bond

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