Modified Fry Cyanation of a Chiral Pyridinium Salt: Asymmetric Syntheses of (–)‐Coniine and (–)‐Solenopsin A

Vu, Van Ha; Jouanno, Laurie-Anne; Cheignon, Adèle; Roisnel, Thierry; Dorcet, Vincent; Sinbandhit, Sourisak; Hurvois, Jean‐Pierre

doi:10.1002/ejoc.201300595

Cited by 12 publications

(8 citation statements)

References 82 publications

(21 reference statements)

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“…Mp = 119–122 °C {lit . mp 119 °C}; [α] D 20 = +76.3° ( c 1.0, chloroform) {lit . [α] D 22 = +78.0° ( c 1.0, chloroform)}; 1 H NMR (500 MHz, CDCl 3 ) δ 7.46 (d, J = 7.3 Hz, 2H), 7.28 (t, J = 7.3 Hz, 2H), 7.21 (t, J = 7.3 Hz, 1H), 4.86 (s, 1H), 2.98 (d, J = 12.5 Hz, 1H), 2.70–2.64 (m, 1H), 2.25–2.20 (m, 1H), 1.69 (d, J = 13.5 Hz, 1H), 1.57–1.51 (m, 3H), 1.29–1.19 (m, 1H), 1.16–1.09 (m, 4H); 13 C{ 1 H} NMR (126 MHz, CDCl 3 ) δ 178.3, 142.6, 128.0, 127.0, 126.6, 74.5, 52.3, 43.8, 30.2, 22.5, 21.8, 19.1. ν max /cm –1 : 3153, 2696, 2590, 2544, 1593, 1491, 1477, 1444, 1381, 1267.…”

Section: Methodssupporting

confidence: 72%

“…(by 1 H NMR in CDCl 3 , 500 MHz). Mp = 119–122 °C {lit . mp 119 °C}; [α] D 20 = +76.3° ( c 1.0, chloroform) {lit .…”

Section: Methodssupporting

confidence: 63%

“…[α] D 22 = +78.0° ( c 1.0, chloroform)}; 1 H NMR (500 MHz, CDCl 3 ) δ 7.46 (d, J = 7.3 Hz, 2H), 7.28 (t, J = 7.3 Hz, 2H), 7.21 (t, J = 7.3 Hz, 1H), 4.86 (s, 1H), 2.98 (d, J = 12.5 Hz, 1H), 2.70–2.64 (m, 1H), 2.25–2.20 (m, 1H), 1.69 (d, J = 13.5 Hz, 1H), 1.57–1.51 (m, 3H), 1.29–1.19 (m, 1H), 1.16–1.09 (m, 4H); 13 C{ 1 H} NMR (126 MHz, CDCl 3 ) δ 178.3, 142.6, 128.0, 127.0, 126.6, 74.5, 52.3, 43.8, 30.2, 22.5, 21.8, 19.1. ν max /cm –1 : 3153, 2696, 2590, 2544, 1593, 1491, 1477, 1444, 1381, 1267. The spectral data correspond to those reported in the literature . HRMS (ESI) m / z : [M – Y ] + Calcd for C 6 H 14 N + 100.112624; Found 100.27 by LCMS, ESI-MS/MS; {lit .…”

Section: Methodsmentioning

confidence: 99%

“…The spectral data correspond to those reported in the literature . HRMS (ESI) m / z : [M – Y ] + Calcd for C 6 H 14 N + 100.112624; Found 100.27 by LCMS, ESI-MS/MS; {lit . HRMS [M – Y ] + : 100.1125}; HRMS (ESI) m / z : [M – X ] − Calcd for C 8 H 7 O 3 – 151.0395; Found 151.02 by LCMS, ESI-MS/MS.…”

Section: Methodsmentioning

confidence: 99%

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Continuous Flow Chiral Amine Racemization Applied to Continuously Recirculating Dynamic Diastereomeric Crystallizations

et al. 2021

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A new, dynamic diastereomeric crystallization method has been developed, in which the mother liquors are continuously separated, racemized over a fixed-bed catalyst, and recirculated to the crystallizer in a resolution−racemization−recycle (R 3 ) process. Separating the racemization from crystallization overcomes problems of using catalysts in situ, that suffer conflicting sets of conditions, inhibition, and separation. Continuous racemization has been achieved through the covalent attachment of [IrCp*I 2 ] 2 SCRAM catalyst to Wang resin solid support to give a fixed-bed catalyst. One tertiary and a variety of secondary optically enriched amines have been racemized efficiently, with residence times compatible with the crystallization (2.25−30 min). The catalyst demonstrates lower turnover (TOF) than the homogeneous analogue but with reuse shows a long lifetime (e.g., 40 recycles, 190 h) giving acceptable turnover number (TON) (up to 4907). The slow release of methylamine during racemization of N-methyl amines was found to inactivate the catalyst, which could be partially reactivated using hydroiodic acid. Dynamic crystallization is achieved in the R 3 process through the continual removal of the more soluble diastereomer and supply of the less soluble one. The solubility of the diastereomers was determined, and the difference correlates to the rate of resolution but is also affected by the rates of racemization, crystal growth, and dissolution. A variety of cyclic and acyclic amine salts were resolved using mandelic acid (MA) and ditoluoyl tartaric acid (DTTA) with higher resolvability (S = yield × d.e.) than the simple diastereomeric crystallization alone. Comparing resolvabilities, resolutions were 1.6−44 times more effective with the R 3 process than batch, though one case was worse. Further investigation of this revealed an unusual thermodynamic switching behavior: rac-N-methylphenethylamine was initially resolved as an (S,S)-bis-alkylammonium tartrate crystal but over time became the equivalent (R,S) salt. Thermal, mixing, concentration, stoichiometry, and seeding conditions were all found to affect the onset of the switching behavior which is only associated with difunctional resolving reagents.

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Section: Methodssupporting

confidence: 72%

“…(by 1 H NMR in CDCl 3 , 500 MHz). Mp = 119–122 °C {lit . mp 119 °C}; [α] D 20 = +76.3° ( c 1.0, chloroform) {lit .…”

Section: Methodssupporting

confidence: 63%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Continuous Flow Chiral Amine Racemization Applied to Continuously Recirculating Dynamic Diastereomeric Crystallizations

et al. 2021

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“…Syntheses are reported in the ESI; † 1b(PF 6 ) was prepared according to a known procedure. 22 The experimental procedures of NMR and UV-vis titrations have been described elsewhere. 23 Titration data were processed with the Hyperquad package 24 to determine the equilibrium constants.…”

Section: Methodsmentioning

confidence: 99%

Novel hydrogen- and halogen-bonding anion receptors based on 3-iodopyridinium units

Amendola

Bergamaschi

Boiocchi³

et al. 2016

RSC Adv.

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Novel tripodal 3-iodopyridinium-based receptors were investigated through (i) UV-vis and NMR titrations with anions in solution, (ii) theoretical calculations, and (iii) X-ray diffraction studies. Their anion binding properties were compared to those of the monobranched model and/or non-halogenated model systems. Investigations in acetonitrile pointed out that the iodine atom in the meta position to pyridinium enhances anion affinity. According to computational studies, this effect seemed to depend on the electron-withdrawing nature of the iodine-substituents. Notably, 1 : 1 adducts were observed to form in solution with all the investigated anions. The strong de-shielding effect observed on the receptors' protons upon anion binding indicated their participation in hydrogen-bonds with the coordinated anion. This result was supported by theoretical calculations and, in the solid state, by X-ray diffraction studies on the complexes with nitrate and bromide. In the crystalline state, the pyridinium arms of the tripodal receptor assume a "2-up, 1-down" conformation. Both nitrate and bromide anions are included in the receptor's cavity, forming two hydrogen-bonding interactions with the protons of the "2-up" arms, and one halogen-bonding interaction with the C-I group of a second molecular cation. The combination of hydrogen and halogen bonds leads to supramolecular chains in the crystals

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Contribution of the Centrifugal Partition Chromatography (CPC) to the Purification of Zincke Reaction Products

et al. 2019

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The Zincke reaction poses a difficulty when attempting to purify the crude mixtures and isolate reaction products in analytically pure form. This paper introduces the successful method of using the centrifugal partition chromatography (CPC) to isolate pyridinium salts garnered by this reaction returning good yields and high degrees of purity. Efficient purifications were obtained by using (n‐BuOH/MeOH/H2O) biphasic solvent systems. The CPC confirmed its suitability for isolating compounds prone to decompose during purification on solid stationary phases. It has also proved to be an efficient method for valorizing incomplete Zincke reactions.

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Modified Fry Cyanation of a Chiral Pyridinium Salt: Asymmetric Syntheses of (–)‐Coniine and (–)‐Solenopsin A

Cited by 12 publications

References 82 publications

Continuous Flow Chiral Amine Racemization Applied to Continuously Recirculating Dynamic Diastereomeric Crystallizations

Continuous Flow Chiral Amine Racemization Applied to Continuously Recirculating Dynamic Diastereomeric Crystallizations

Novel hydrogen- and halogen-bonding anion receptors based on 3-iodopyridinium units

Contribution of the Centrifugal Partition Chromatography (CPC) to the Purification of Zincke Reaction Products

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