Ambident nucleophilic reactivity. 9. Regioselectivity in the reaction of ambident phenoxide ion and methoxide and hydroxide ions with 2,4,6-trinitroanisole. Kinetic and thermodynamic control

1992 ◽  
Vol 114 (14) ◽  
pp. 5610-5619 ◽  
Author(s):  
Erwin Buncel ◽  
Julian M. Dust ◽  
Andrzej Jonczyk ◽  
Richard A. Manderville ◽  
Ikenna Onyido
Keyword(s):  
Thermodynamic Control ◽  
Nucleophilic Reactivity

Ambident nucleophilic reactivity in σ-complex formation. Part 5. Reaction of 1-phenyl-2,4,6-trinitrobenzene with methoxide and phenoxide ions

1984 ◽  
Vol 62 (3) ◽  
pp. 534-539 ◽  
Author(s):  
Erwin Buncel ◽  
Suresh Kumar Murarka ◽  
Albert Richard Norris
Keyword(s):  
Complex Formation ◽  
Kinetic Control ◽  
Thermodynamic Control ◽  
Electronic Effects ◽  
Strain Relief ◽  
Methanol Solutions ◽  
Nucleophilic Reactivity

The reactions of 1-phenyl-2,4,6-trinitrobenzene (4) with methoxide and phenoxide ions in DMSO and DMSO–methanol solutions have been investigated. MeO− gives rise to a 1,3 adduct through kinetic control and a 1,1 adduct through thermodynamic control. These processes persist also in the reaction of 4 with potassium phenoxide in DMSO–methanol. However, reaction of 4 with potassium phenoxide in DMSO gives rise to a 1,3 adduct as the only observed species in which phenoxide is bonded to the nitroaromatic moiety via the para phenoxy carbon, in accord with previous observations on the ambident reactivity of phenoxide ion. The results are considered in terms of various steric and electronic effects and it is concluded that F-strain, relief of steric compression, and delocalizability considerations play dominant roles in accounting for the observed reaction course.

Stereodivergent Alkyne Hydrofluorination Using a Simple Practical Reagent

2020 ◽  
Author(s):  
Rui Guo ◽  
Xiaotian Qi ◽  
Hengye Xiang ◽  
Paul Geaneoates ◽  
Ruihan Wang ◽  
...  
Keyword(s):  
Bond Formation ◽  
Biologically Active ◽  
Dft Studies ◽  
Thermodynamic Control ◽  
Important Goal ◽  
Peptide Bonds ◽  
Metal Free ◽  
Vinyl Cation ◽  
E And Z Isomers ◽  
Vinyl Fluorides

Vinyl fluorides play an important role in drug development as they serve as bioisosteres for peptide bonds and are found in a range of biologically active molecules. The discovery of safe, general and practical procedures to prepare vinyl fluorides remains an important goal and challenge for synthetic chemistry. Here we introduce an inexpensive and easily-handled reagent and report simple, scalable, and metal-free protocols for the regioselective and stereodivergent hydrofluorination of alkynes to access both the E and Z isomers of vinyl fluorides. These conditions were suitable for a diverse collection of alkynes, including several highly-functionalized pharmaceutical derivatives. Mechanistic and DFT studies support C–F bond formation through a vinyl cation intermediate, with the (E)- and (Z)-hydrofluorination products forming under kinetic and thermodynamic control, respectively.<br>

A side-on Mn(iii)–peroxo supported by a non-heme pentadentate N3Py2 ligand: synthesis, characterization and reactivity studies

2021 ◽  
Author(s):  
Dattaprasad D. Narulkar ◽  
Azaj Ansari ◽  
Anil Kumar Vardhaman ◽  
Sarvesh S. Harmalkar ◽  
Giribabu Lingamallu ◽  
...  
Keyword(s):  
Nucleophilic Reactivity ◽  
Ligand Synthesis ◽  
Aldehyde Oxidation

A new non-heme Mn(iii)–peroxo (1a) has been generated, characterized and reactivity is in aldehyde deformylation reaction. A nucleophilic reactivity of 1a in aldehyde oxidation is proposed.

scholarly journals Computational exploration of heterometal substitution into the decaniobate framework, [Nb10O28]6−

2021 ◽  
Author(s):  
C. André Ohlin
Keyword(s):  
Spin State ◽  
Thermodynamic Control ◽  
Computational Exploration

The relative energetics of isomers of [MzNb9O28]11−z− is investigated computationally; new synthetic targets are identified, thermodynamic control is discussed, and prediction of spin state is investigated.

scholarly journals Mechanism of loss of thermodynamic control in mitochondria due to hyperthyroidism and temperature.

1992 ◽  
Vol 267 (22) ◽  
pp. 15348-15355
Author(s):  
S Luvisetto ◽  
I Schmehl ◽  
E Intravaia ◽  
E Conti ◽  
G.F. Azzone
Keyword(s):  
Thermodynamic Control
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