Catalytic, Enantioselective 1,2-Difluorination of Cinnamamides

Organic Letters, Journal Year: 2019, Volume and Issue: 21(13), P. 4919 - 4923

Published: April 9, 2019

The enantio- and diastereoselective synthesis of 1,2-difluorides via chiral aryl iodide-catalyzed difluorination cinnamamides is reported. method uses HF-pyridine as a fluoride source mCPBA stoichiometric oxidant to turn over catalyst, affords compounds containing vicinal, fluoride-bearing stereocenters. Selectivity for 1,2-difluorination versus rearrangement pathway resulting in 1,1-difluorination enforced through anchimeric assistance from N- tert-butyl amide substituent.

Language: Английский

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Hyperconjugation

Wiley Interdisciplinary Reviews Computational Molecular Science, Journal Year: 2018, Volume and Issue: 9(2)

Published: Sept. 6, 2018

This review outlines the role of hyperconjugative interactions in structure and reactivity organic molecules. After defining common patterns, we discuss main factors controlling magnitude effects, including orbital symmetry, energy gap, electronegativity, polarizability. The danger underestimating contribution are illustrated by a number spectroscopic, conformational, structural effects. stereoelectronic nature hyperconjugation offers useful ways for control molecular stability reactivity. New manifestations effects continue to be uncovered theory experiments. article is categorized under: Structure Mechanism > Molecular Structures Software Modeling Reaction Mechanisms Catalysis

Language: Английский

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Revisiting pesticide pollution: The case of fluorinated pesticides

Environmental Pollution, Journal Year: 2021, Volume and Issue: 292, P. 118315 - 118315

Published: Oct. 9, 2021

Language: Английский

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Fluorinated Rings: Conformation and Application

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(25), P. 7193 - 7213

Published: Jan. 29, 2021

The introduction of fluorine atoms into molecules and materials across many fields academic industrial research is now commonplace, owing to their unique properties. A particularly interesting feature the impact substitution on relative orientation a C-F bond when incorporated organic molecules. In this Review, we will be discussing conformational behavior fluorinated aliphatic carbo- heterocyclic systems. preference each system associated with various interactions introduced by such as charge-dipole, dipole-dipole, hyperconjugative interactions. contribution interaction stabilization alicyclic system, which manifests itself in low conformations, discussed detail. novelty demonstrated presenting most recent applications.

Language: Английский

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Expanding organofluorine chemical space: the design of chiral fluorinated isosteres enabled by I(i)/I(iii) catalysis

Chemical Science, Journal Year: 2021, Volume and Issue: 12(32), P. 10686 - 10695

Published: Jan. 1, 2021

Short aliphatic groups are prevalent in bioactive small molecules and play an essential role regulating physicochemistry molecular recognition phenomena.

Language: Английский

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Regio‐ and Enantioselective Intermolecular Aminofluorination of Alkenes via Iodine(I)/Iodine(III) Catalysis**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(32)

Published: May 18, 2022

The regio- and enantio-selective, intermolecular vicinal fluoroamination of α-trifluoromethyl styrenes has been achieved by enantioselective I

Language: Английский

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Linkage-Editing Pseudo-Glycans: A Reductive α-Fluorovinyl-C-Glycosylation Strategy to Create Glycan Analogs with Altered Biological Activities

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 2237 - 2247

Published: Jan. 10, 2024

The acetal (O-glycoside) bonds of glycans and glycoconjugates are chemically biologically vulnerable, therefore C-glycosides interest as more stable analogs. We hypothesized that, if the O-glycoside linkage plays a vital role in glycan function, biological activities C-glycoside analogs would vary depending on their substituents. Based this idea, we adopted "linkage-editing strategy" for creation (pseudo-glycans). designed three types pseudo-glycans with CH2 CHF linkages, which resemble terms bond lengths, angles, bulkiness, synthesized them efficiently by means fluorovinyl C-glycosylation selective hydrogenation reactions. Application strategy to isomaltose (IM), an inducer amylase expression, α-GalCer, activates iNKT cells, resulted discovery CH2-IM, shows increased production ability, CHF-α-GalCer, activity opposite that native serving antagonist cells.

Language: Английский

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Stereodivergent Synthesis of the Vicinal Difluorinated Tetralin of Casdatifan Enabled by Ru-Catalyzed Transfer Hydrogenation

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

We disclose a stereodivergent strategy to prepare vicinal difluorinated tetralins from γ-substituted tetralones via combination of catalyst-controlled transfer hydrogenation and substrate-controlled fluorinations. This process is easily scalable amenable highly functionalized substrates, as demonstrated here in the late-stage synthesis casdatifan, clinical-stage inhibitor hypoxia-inducible factor-2α. Analysis physicochemical properties which features cis-vicinal difluoride, revealed higher level facial polarization compared its trans-vicinal difluoride isomers.

Language: Английский

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Deconstructing the Catalytic, Vicinal Difluorination of Alkenes: HF-Free Synthesis and Structural Study of p-TolIF₂

The Journal of Organic Chemistry, Journal Year: 2017, Volume and Issue: 82(22), P. 11792 - 11798

Published: July 28, 2017

Recently, contemporaneous strategies to achieve the vicinal difluorination of alkenes via an I(I)/I(III) catalysis manifold were independently reported by this laboratory and Jacobsen co-workers. Both proceed through a transient ArI(III)F2 species generated oxidation ArI catalyst. Herein, efficient synthesis p-TolIF2 from p-TolI Selectfluor is presented, together with crystallographic spectroscopic study. To mitigate safety concerns simplify reaction execution, HF-free protocol was devised employing CsF as substitute fluoride source. The study provides insight into initial I(I)→I(III) stage catalytic using Selectfluor.

Language: Английский

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Fluorine Gauche Effect Explained by Electrostatic Polarization Instead of Hyperconjugation: An Interacting Quantum Atoms (IQA) and Relative Energy Gradient (REG) Study

The Journal of Physical Chemistry A, Journal Year: 2018, Volume and Issue: 122(5), P. 1439 - 1450

Published: Jan. 30, 2018

We present an interacting quantum atoms (IQA) study of the gauche effect by comparing 1,2-difluoroethane, 1,2-dichloroethane, and three conformers 1,2,3,4,5,6-hexafluorocyclohexane. In is observed in that conformation more stable than anti, whereas 1,2-dichloroethane opposite true. The analysis performed here exhaustive unbiased thanks to using recently introduced relative energy gradient (REG) method [ Thacker , J. C. R. ; Popelier P. L. A. Theor. Chem. Acc . 2017 136 86 ], as implemented in-house program ANANKE. challenge common explanation hyperconjugation responsible for stability 1,2-difluoroethane instead electrostatics cause stability. Our also seen other molecules displaying local conformations, such synthesized "all-cis" hexafluorocyclohexane its where all fluorine are equatorial positions. Using our extension traditional IQA methodology allows partitioning electrostatic terms into polarization charge transfer, we propose 1,3 C···F interactions. words, if a number aligned, then due nearby carbon increased.

Language: Английский

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