Quantum Mechanical Transition-State Analysis Reveals the Precise Origin of Stereoselectivity in Chiral Quaternary Cinchonidinium Phase-Transfer Catalyzed Enolate Allylation

Cook, Thomas C; Andrus, Merritt B.; Ess, Daniel H.

doi:10.1021/ol3026582

Cited by 32 publications

(15 citation statements)

References 21 publications

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“…(2H, s), 6.76 (1H, s), 2.38 (3H, s). 13 C-NMR (68 MHz, CDCl3) δ: 139.9, 130.1, 128.5, 121.8 (q, J = 274.9…”

Section: 1'-(5-methyl-13-phenylene)bis(222-trifluoroethanone)mentioning

confidence: 99%

“…H-NMR (270 MHz, CDCl3) δ: 7.90 (4H, m,), 7.41-7.13 (7H, m), 2.52-2.41 (9H, m) 13. C-NMR (68 MHz, CDCl3) δ: 179.5 (q, J = 36.3 Hz), 140.8, 136.5, 136.5, 130.8, 128.7, 128.7, 128.7, 116.3 (q, J = 291.3 Hz), 21.3 (3C).…”

mentioning

confidence: 99%

“…Hz), 1.45 (9H, s) 13. C-NMR (68 MHz, CDCl3) δ: 171.1, 169.9, 140.8, 138.8, 136.0, 128.6, 128.2, 127.9, 127.2, 122.5, 121.7 (q, J = 274.9 Hz), 81.6, 66.8, 39.2, 28.0 (q, J = 40.8 Hz), 27.9.…”

mentioning

confidence: 99%

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Design and Synthesis of 1,3-Bis(3-(trifluoromethyl)diazirin-3-yl)phenylalanine for Efficient Photo Cross-Linking

Murai¹,

Hashimoto²,

Yoshida³

et al. 2022

HETEROCYCLES

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Photoreactive a-amino acids are powerful chemical tools for elucidating interactions in protein networks. Typically, photophores are required for stability and generation of high-reactive species. Additionally, orientation of photophores is one of the significant issues for performing photoaffinity labeling.Therefore, we rationally designed a bis-diazirinyl-phenylalanine for which photo cross-linking efficiency could be increased. In this study, we synthesized a new 1,3-bis(3-(trifluoromethyl)diazirin-3-yl)phenylalanine and demonstrated further study in terms of photoactivation.Elucidation of target biomolecules of a bioactive compound is invaluable in the field of life science for a deep understanding of complex biological mechanisms. Various strategies including a genetic approach and 3D structure determination involving solution-state NMR and X-ray crystallography have been used for that purpose. Although these approaches can provide detailed information on the structure of a target biomolecule, an abundant pure molecule is required. As an alternative method, affinity-based chemical probes have been used to identify and visualize target biomolecules in complex systems. Photoaffinity labeling is one of the powerful chemical approaches used for identifying the interaction, where it can conduct binding site mapping, protein-protein interaction and visualizes live-cell imaging by a photoinduced covalent bond between a ligand and its target molecule. 1 The selection of photophores is

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“…(2H, s), 6.76 (1H, s), 2.38 (3H, s). 13 C-NMR (68 MHz, CDCl3) δ: 139.9, 130.1, 128.5, 121.8 (q, J = 274.9…”

Section: 1'-(5-methyl-13-phenylene)bis(222-trifluoroethanone)mentioning

confidence: 99%

mentioning

confidence: 99%

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Design and Synthesis of 1,3-Bis(3-(trifluoromethyl)diazirin-3-yl)phenylalanine for Efficient Photo Cross-Linking

Murai¹,

Hashimoto²,

Yoshida³

et al. 2022

HETEROCYCLES

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“…It is well-known that the theoretical chemistry can offer alternative opportunity to study the mechanism, especially the untouchable transition states, besides experimental procedures. Recently, overcoming the large and flexible disadvantage of cinchona-derived PTC catalysts, some calculations were performed to throw new insights on PTC reactions. − Lipkowitz and O’Donnell conducted a precedent theoretical study on the interaction between the N -benzylcinchoninium cation and Schiff base-derived enolates with molecular dynamics and semiempirical quantum theory in 1991 . They found the Z -enolates selective binding on the front side of the N -benzylcinchoninium may account for the observed enantioselectivity.…”

Section: Introductionmentioning

confidence: 99%

Origin of Stereoselectivity of the Photoinduced Asymmetric Phase-Transfer-Catalyzed Perfluoroalkylation of β-Ketoesters

Yang

Zhang

et al. 2017

J. Org. Chem.

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The sources of asymmetric induction in the photoinduced phase-transfer-catalytic perfluoroalkylation of β-ketoesters were interpreted by density functional theory calculations. The calculations indicated that multiple hydrogen-bonding interactions mode rather than π-π stacking interactions model better described the transition structure of the reaction. The quantitative estimation of these noncovalent interactions within the key transition states identified that the O-H···O and specific C-H···O hydrogen bonds play key roles for the stereocontrol.

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“…NOE correlations study of PTC 2 with borohydride ion 6 indicated the borohydride occupies the F1 face of PTC 2. Computational simulation 7 also described the stable transition states where an enolate locates on the F1 face.…”

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confidence: 99%

Dimeric cinchona ammonium salts with benzophenone linkers: enantioselective phase transfer catalysts for the synthesis of α-amino acids

et al. 2018

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Quantum Mechanical Transition-State Analysis Reveals the Precise Origin of Stereoselectivity in Chiral Quaternary Cinchonidinium Phase-Transfer Catalyzed Enolate Allylation

Cited by 32 publications

References 21 publications

Design and Synthesis of 1,3-Bis(3-(trifluoromethyl)diazirin-3-yl)phenylalanine for Efficient Photo Cross-Linking

Design and Synthesis of 1,3-Bis(3-(trifluoromethyl)diazirin-3-yl)phenylalanine for Efficient Photo Cross-Linking

Origin of Stereoselectivity of the Photoinduced Asymmetric Phase-Transfer-Catalyzed Perfluoroalkylation of β-Ketoesters

Dimeric cinchona ammonium salts with benzophenone linkers: enantioselective phase transfer catalysts for the synthesis of α-amino acids

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