Expedient Synthesis of Chiral Oxazolidinone Scaffolds via Rhodium-Catalyzed Asymmetric Ring-Opening with Sodium Cyanate

Tsui, Gavin Chit; Ninnemann, Nina M.; Hosotani, Akihito; Lautens, Mark

doi:10.1021/ol4000668

Cited by 61 publications

(22 citation statements)

References 32 publications

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“…Ring‐opening of epoxides using nitrogen‐containing nucleophile such as azide and amines affords a convenient methodology for C−N bond formation . Chemical ring‐opening of epoxides with these nucleophiles has been widely studied, while the work on the reaction with inorganic cyanate is very rare . Herein the synthesis of chiral 5‐aryl‐2‐oxazolidinones via enantio‐ and regioselective ring‐opening of styrene oxides was developed, which showed some greener advantages than previous method .…”

Section: Methodsmentioning

confidence: 99%

“…[17] Chemical ring-opening of epoxides with these nucleophiles has been widely studied, while the work on the reaction with inorganic cyanate is very rare. [18] Herein the synthesis of chiral 5-aryl-2-oxazolidinones via enantio-and regioselective ring-opening of styrene oxides was developed, which showed some greener . Catalytic triad Ser132-Tyr145-Arg149, (R)-1 a and (S)-1 a were showed as sticks.…”

Section: Updates Ascwiley-vchdementioning

confidence: 99%

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Synthesis of Chiral 5‐Aryl‐2‐oxazolidinones via Halohydrin Dehalogenase‐Catalyzed Enantio‐ and Regioselective Ring‐Opening of Styrene Oxides

Wan

Zhou

et al. 2020

Adv Synth Catal

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An efficient biocatalytic approach for enantio‐ and regioselective ring‐opening of styrene oxides with cyanate was developed by using the halohydrin dehalogenase HheC from Agrobacterium radiobacter AD1, generating the corresponding chiral 5‐aryl‐2‐oxazolidinones in up to 47% yield and 90% ee. Additionally, the origin of enantioselectivity and regioselectivity of the HheC‐catalyzed cyanate‐mediated ring‐opening process was uncovered by single enantiomer bioconversions and molecular docking study.

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Section: Methodsmentioning

confidence: 99%

Section: Updates Ascwiley-vchdementioning

confidence: 99%

Synthesis of Chiral 5‐Aryl‐2‐oxazolidinones via Halohydrin Dehalogenase‐Catalyzed Enantio‐ and Regioselective Ring‐Opening of Styrene Oxides

Wan

Zhou

et al. 2020

Adv Synth Catal

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“…For the biological activity of oxazolidinone derivatives, see: Michalska et al (2012); Mathur et al (2013); Jindal et al (2013). For related structures, see: Bach et al (2001); Tsui et al (2013). For detailed of the synthesis, see: Madesclaire et al (2013).…”

Section: Related Literaturementioning

confidence: 99%

(4S)-4-[(R)-Chloro(4-nitrophenyl)methyl]-1,3-oxazolidin-2-one

Gaumet¹,

Denis²,

Madesclaire³

et al. 2013

Acta Cryst E

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In the title compound, C10H9ClN2O4, the oxazolidinone ring adopts a near-planar conformation, with mean and maximum deviations of 0.0204 (8) and 0.0328 (8) Å, respectively. The nitro group is twisted slightly from the plane of the benzene ring, making a dihedral angle of 6.79 (3)°. The dihedral angle between the mean oxazolidinone plane and the benzene ring is 56.21 (3)°. In the crystal, N—H⋯O hydrogen bonds and N—O⋯π interactions [O⋯centroid distances = 3.478 (1) and 3.238 (1) Å] dominate the packing, forming infinite zigzag chains along the b-axis direction. Neighbouring chains are linked together through C—H⋯O and C—H⋯Cl interactions. The absolute configuration of the two stereogenic centres was determined using the anomalous dispersion of the Cl atom.

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“…Amines are initially activated by forming a carbamate or isocyanate, followed by ring‐closure via C−O bond formation. New methods, using less common substrates, are still of interest to synthetic chemists . Oxazolidinone 5 (Scheme ) has recently attracted our attention as an API (active pharmaceutical ingredient) precursor.…”

Section: Introductionmentioning

confidence: 99%

Continuous Flow Photochemical Benzylic Bromination of a Key Intermediate in the Synthesis of a 2‐Oxazolidinone

Chen

Frutos²,

Mateos³

et al. 2018

ChemPhotoChem

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A continuous flow procedure for the benzylic photobromination of methyl N,N‐bis (tert‐butoxycarbonyl) phenylalaninate is presented. This photochemical transformation generating the brominated intermediate is the critical step in the synthesis of the oxazolidinone methyl (4S,5R)‐3‐N‐tert‐Butoxycarbonyl‐5‐phenyl‐1,3‐oxazolidin‐2‐oxo‐4‐carboxylate, a key intermediate for the preparation of active pharmaceutical ingredients. The reaction was optimized in three continuous flow photoreactors: A self‐made reactor based on a T5 8 W black light lamp, as well as the commercially available VapourTec® UV‐150 and Corning® Advanced‐Flow™ reactors, both equipped with LED light sources. Under optimal conditions, concentrated solutions (95 g/L) of the starting material could be processed on a multi‐gram scale, providing high conversion (96 %) within 7 min at 30 °C, using 2 equivalents of N‐bromosuccinimide (NBS).

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Expedient Synthesis of Chiral Oxazolidinone Scaffolds via Rhodium-Catalyzed Asymmetric Ring-Opening with Sodium Cyanate

Cited by 61 publications

References 32 publications

Synthesis of Chiral 5‐Aryl‐2‐oxazolidinones via Halohydrin Dehalogenase‐Catalyzed Enantio‐ and Regioselective Ring‐Opening of Styrene Oxides

Synthesis of Chiral 5‐Aryl‐2‐oxazolidinones via Halohydrin Dehalogenase‐Catalyzed Enantio‐ and Regioselective Ring‐Opening of Styrene Oxides

(4S)-4-[(R)-Chloro(4-nitrophenyl)methyl]-1,3-oxazolidin-2-one

Continuous Flow Photochemical Benzylic Bromination of a Key Intermediate in the Synthesis of a 2‐Oxazolidinone

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