Enantioselective synthesis of the essential oil and pheromonal component ar-himachalene by a chiral pool and chirality induction approach

Khatod, Harshali S.

doi:10.1016/j.tetasy.2012.09.008

Cited by 27 publications

(27 citation statements)

References 31 publications

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“…Furthermore, we show that chirality is induced into the achiral plasmonic surface of the substrate by enantiomeric analytes. This is a new phenomenon of chirality induction that is fundamentally different to previously reported mechanisms [23][24][25][26][27][28][29] . We observe a symmetry breaking of surface plasmons interacting with a resonant dye molecule once they are tethered to chiral molecules.…”

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confidence: 74%

Through-space transfer of chiral information mediated by a plasmonic nanomaterial

et al. 2015

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The ability to detect chirality gives stereochemically attuned nanosensors the potential to revolutionize the study of biomolecular processes. Such devices may structurally characterize the mechanisms of protein-ligand binding, the intermediates of amyloidogenic diseases and the effects of phosphorylation and glycosylation. We demonstrate that single nanoparticle plasmonic reporters, or nanotags, can enable a stereochemical response to be transmitted from a chiral analyte to an achiral benzotriazole dye molecule in the vicinity of a plasmon resonance from an achiral metallic nanostructure. The transfer of chirality was verified by the measurement of mirror image surface enhanced resonance Raman optical activity spectra for the two enantiomers of both ribose and tryptophan. Computational modelling confirms these observations and reveals the novel chirality transfer mechanism responsible. This is the first report of colloidal metal nanoparticles in the form of single plasmonic substrates displaying an intrinsic chiral sensitivity once attached to a chiral molecule.

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confidence: 74%

Through-space transfer of chiral information mediated by a plasmonic nanomaterial

et al. 2015

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“…c , Applications in asymmetric total syntheses of terpenoids. It is known that α-tetralone ( 2b ) is an intermediate for accessing erogorgiaene 20,21 , ( R )-ar-himachalene 22 and (−)-heliophenanthrone 23 in three to seven steps (shown at the bottom). However, enantioselective preparation of α-tetralones with a C4 stereocentre is non-trivial and generally requires many steps 22 (top left, pale grey).…”

Section: Figurementioning

confidence: 99%

“…It is known that α-tetralone ( 2b ) is an intermediate for accessing erogorgiaene 20,21 , ( R )-ar-himachalene 22 and (−)-heliophenanthrone 23 in three to seven steps (shown at the bottom). However, enantioselective preparation of α-tetralones with a C4 stereocentre is non-trivial and generally requires many steps 22 (top left, pale grey). In our technique (top right, dark grey), we synthesized optically enriched 3-arylcyclopentanones in a single step through asymmetric conjugate addition of cyclopentenone and arylboronic acids 24 ; then, using our C–C activation approach, we isolated α-tetralone ( ( R )-2b ) in 64% yield over two steps, with 94.5% chirality transfer.…”

Section: Figurementioning

confidence: 99%

Catalytic activation of carbon–carbon bonds in cyclopentanones

Xia

Lü

Liu

et al. 2016

Nature

231

104

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In the chemical industry, molecules of interest are based primarily on carbon skeletons. When synthesizing such molecules, the activation of carbon–carbon single bonds (C–C bonds) in simple substrates is strategically important: it offers a way of disconnecting such inert bonds, forming more active linkages (for example, between carbon and a transition metal) and eventually producing more versatile scaffolds1–13. The challenge in achieving such activation is the kinetic inertness of C–C bonds and the relative weakness of newly formed carbon–metal bonds6,14. The most common tactic starts with a three- or four-membered carbon-ring system9–13, in which strain release provides a crucial thermodynamic driving force. However, broadly useful methods that are based on catalytic activation of unstrained C–C bonds have proven elusive, because the cleavage process is much less energetically favourable. Here we report a general approach to the catalytic activation of C–C bonds in simple cyclopentanones and some cyclohexanones. The key to our success is the combination of a rhodium pre-catalyst, an N-heterocyclic carbene ligand and an amino-pyridine co-catalyst. When an aryl group is present in the C3 position of cyclopentanone, the less strained C–C bond can be activated; this is followed by activation of a carbon–hydrogen bond in the aryl group, leading to efficient synthesis of functionalized α-tetralones—a common structural motif and versatile building block in organic synthesis. Furthermore, this method can substantially enhance the efficiency of the enantioselective synthesis of some natural products of terpenoids. Density functional theory calculations reveal a mechanism involving an intriguing rhodium-bridged bicyclic intermediate.

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“…Finally, Friedel-Crafts acylation gave the desired tetralone 6 with 99.5 % ee. This tetralone is, for example, an intermediate in the total synthesis of (À)-laevigatin, [14] (S)-ar-himachalene, [15] and (+)-erogorgiaene. [16] Starting from A1, we also considered the possibility of accessing acyclic natural compounds.…”

Section: Methodsmentioning

confidence: 99%

Enantioselective Copper‐Catalyzed Conjugate Addition of Trimethylaluminum to β,γ‐Unsaturated α‐Ketoamides: Efficient Access to γ‐Methyl‐Substituted Carbonyl Compounds

Goncalves-Contal¹,

Gremaud²,

Alexakis³

2013

Angew Chem Int Ed

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Picture perfect: By using the reagent trimethylaluminium and β,γ-unsaturated α-ketoamides, 1,4-adducts were obtained with perfect 1,4-regioselectivity and good to excellent yields and ee values. The potential synthetic utility of the methodology was highlighted by preparation of γ-methyl-substituted carbonyls, key synthons to many natural products. binap=2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, TC=thiophene carboxylate

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Enantioselective synthesis of the essential oil and pheromonal component ar-himachalene by a chiral pool and chirality induction approach

Cited by 27 publications

References 31 publications

Through-space transfer of chiral information mediated by a plasmonic nanomaterial

Through-space transfer of chiral information mediated by a plasmonic nanomaterial

Catalytic activation of carbon–carbon bonds in cyclopentanones

Enantioselective Copper‐Catalyzed Conjugate Addition of Trimethylaluminum to β,γ‐Unsaturated α‐Ketoamides: Efficient Access to γ‐Methyl‐Substituted Carbonyl Compounds

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