Analysis of transition state stabilization by non-covalent interactions in organocatalysis: application of atomic and functional-group partitioned symmetry-adapted perturbation theory to the addition of organoboron reagents to fluoroketones

2018 ◽  
Vol 20 (27) ◽  
pp. 18241-18251 ◽  
Author(s):  
Brandon W. Bakr ◽  
C. David Sherrill
Keyword(s):  
Perturbation Theory ◽  
Transition State ◽  
Functional Group ◽  
Transition State Stabilization ◽  
Non Covalent Interactions ◽  
Covalent Interactions

Enantioselectivity is examined in the addition of allyl groups to fluorinated ketones.

scholarly journals Symmetry-Adapted Perturbation Theory Decomposition of the Reaction Force: Insights into Substituent Effects Involved in Hemiacetal Formation Mechanisms

2019 ◽  
Author(s):  
Wallace Derricotte
Keyword(s):  
Perturbation Theory ◽  
Functional Group ◽  
Reaction Force ◽  
Substituent Effects ◽  
Formation Mechanisms ◽  
Lower Activation ◽  
Non Covalent Interactions ◽  
Force Components ◽  
Covalent Interactions ◽  
Lower Activation Energy

<div>The decomposition of the reaction force based on symmetry-adapted perturbation theory (SAPT) has been proposed. This approach was used to investigate the subtituent effects along the reaction coordinate pathway for the hemiacetal formation mechanism between methanol and substituted aldehydes of the form CX<sub>3</sub>CHO (X = H, F, Cl, and Br), providing a quantitative evaluation of the reaction-driving and reaction-retarding force components. Our results highlight the importance of more favorable electrostatic and induction effects in the reactions involving halogenated aldehydes that leads to lower activation energy barriers. These substituent effects are further elucidated by applying the functional-group partition of symmetry-adapted</div><div>perturbation theory (F-SAPT). The results show that the reaction is largely driven by favorable direct non-covalent interactions between the CX<sub>3</sub> group on the aldehyde and the OH group on methanol.</div>

scholarly journals Symmetry-Adapted Perturbation Theory Decomposition of the Reaction Force: Insights into Substituent Effects Involved in Hemiacetal Formation Mechanisms

2019 ◽  
Author(s):  
Wallace Derricotte
Keyword(s):  
Perturbation Theory ◽  
Functional Group ◽  
Reaction Force ◽  
Substituent Effects ◽  
Formation Mechanisms ◽  
Lower Activation ◽  
Non Covalent Interactions ◽  
Force Components ◽  
Covalent Interactions ◽  
Lower Activation Energy

<div>The decomposition of the reaction force based on symmetry-adapted perturbation theory (SAPT) has been proposed. This approach was used to investigate the subtituent effects along the reaction coordinate pathway for the hemiacetal formation mechanism between methanol and substituted aldehydes of the form CX<sub>3</sub>CHO (X = H, F, Cl, and Br), providing a quantitative evaluation of the reaction-driving and reaction-retarding force components. Our results highlight the importance of more favorable electrostatic and induction effects in the reactions involving halogenated aldehydes that leads to lower activation energy barriers. These substituent effects are further elucidated by applying the functional-group partition of symmetry-adapted</div><div>perturbation theory (F-SAPT). The results show that the reaction is largely driven by favorable direct non-covalent interactions between the CX<sub>3</sub> group on the aldehyde and the OH group on methanol.</div>

scholarly journals Functional group interaction profiles: a general treatment of solvent effects on non-covalent interactions

2020 ◽  
Vol 11 (17) ◽  
pp. 4456-4466 ◽  
Author(s):  
Mark D. Driver ◽  
Mark J. Williamson ◽  
Joanne L. Cook ◽  
Christopher A. Hunter
Keyword(s):  
Free Energy ◽  
Solvent Effects ◽  
Functional Group ◽  
Group Interaction ◽  
General Treatment ◽  
Effect Of Solvent ◽  
Non Covalent Interactions ◽  
Covalent Interactions ◽  
Quantitative Tool

Functional group interaction profiles are a quantitative tool for predicting the effect of solvent on the free energy changes associated with non-covalent interactions.

Synthesis of unsymmetrical porphyrin triad containing three different porphyrin subunits assembled by covalent and non-covalent interactions

2008 ◽  
Vol 12 (09) ◽  
pp. 1030-1040 ◽  
Author(s):  
Sokkalingam Punidha ◽  
Smita Rai ◽  
Mangalampalli Ravikanth
Keyword(s):  
Building Block ◽  
Functional Group ◽  
Photophysical Properties ◽  
Time Resolved Fluorescence ◽  
Efficient Energy Transfer ◽  
Time Resolved ◽  
Fluorescence Studies ◽  
Efficient Energy ◽  
Non Covalent Interactions ◽  
Covalent Interactions

Cis-21,23-dithiaporphyrin building block containing one iodophenyl and one pyridyl functional group at meso positions was synthesized by condensing unsymmetrical thiophene diol and symmetrical 16-thiatripyrrin under refluxing propionic acid conditions. The 21,23-dithiaporphyrin building block was coupled with mono-functionalized 21-thiaporphyrin building block containing meso-phenylethyne functional group under mild Pd (0) coupling conditions. The steady-state and time-resolved fluorescence studies support an efficient energy transfer in the singlet excited state from N 3 S porphyrin subunit to N 2 S 2 porphyrin subunit in the dyad. The N 3 S - N 2 S 2 porphyrin dyad was then treated with RuTPP ( CO )( EtOH ) in toluene at refluxing temperature and purified by column chromatography to afford a porphyrin triad containing N 3 S , N 2 S 2 and RuN 4 porphyrin subunits assembled using both covalent and non-covalent interactions. The photophysical properties showed the fluorescence quenching of N 3 S and N 2 S 2 porphyrin subunits in triad due to heavy ruthenium ion which was coordinated to meso-pyridyl ' N ' of N 2 S 2 porphyrin subunit of porphyrin triad.

scholarly journals Crystal structures ofp-substituted derivatives of 2,6-dimethylbromobenzene with ½ ≤Z′ ≤ 4

2016 ◽  
Vol 72 (12) ◽  
pp. 1762-1767
Author(s):  
Angélica Navarrete Guitérrez ◽  
Gerardo Aguirre Hernández ◽  
Sylvain Bernès
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Crystal Structures ◽  
Functional Group ◽  
Molecular Symmetry ◽  
Asymmetric Unit ◽  
Structure Feature ◽  
Non Covalent Interactions ◽  
Derivatives Of ◽  
Covalent Interactions

The crystal structures of four bromoarenes based on 2,6-dimethylbromobenzene are reported, which are differentiated according the functional groupXplacedparato the Br atom:X= CN (4-bromo-3,5-dimethylbenzonitrile, C9H8BrN), (1),X= NO2(2-bromo-1,3-dimethyl-5-nitrobenzene, C8H8BrNO2), (2),X= NH2(4-bromo-3,5-dimethylaniline, C8H10BrN), (3) andX= OH (4-bromo-3,5-dimethylphenol, C8H9BrO), (4). The content of the asymmetric unit is different in each crystal,Z′ = ½ (X= CN),Z′ = 1 (X= NO2),Z′ = 2 (X= NH2), andZ′ = 4 (X= OH), and is related to the molecular symmetry and the propensity ofXto be involved in hydrogen bonding. In none of the studied compounds does the crystal structure feature other non-covalent interactions, such as π–π, C—H...π or C—Br...Br contacts.

scholarly journals Parametrization of Non-covalent Interactions for Transition State Interrogation Applied to Asymmetric Catalysis

2017 ◽  
Vol 139 (20) ◽  
pp. 6803-6806 ◽  
Author(s):  
Manuel Orlandi ◽  
Jaime A. S. Coelho ◽  
Margaret J. Hilton ◽  
F. Dean Toste ◽  
Matthew S. Sigman
Keyword(s):  
Transition State ◽  
Asymmetric Catalysis ◽  
Non Covalent Interactions ◽  
Covalent Interactions

Non‐Covalent Interactions in the Biphenyl Crystal: Is the Planar Conformer a Transition State?

2021 ◽  
Author(s):  
Jesús Hernández-Trujillo ◽  
Bruno Landeros-Rivera ◽  
Vojtech Jancik ◽  
Rafael Moreno-Esparza ◽  
Diego Martínez Otero
Keyword(s):  
Transition State ◽  
Non Covalent Interactions ◽  
Covalent Interactions ◽  
Planar Conformer
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