Computational Study of the Mechanism of the Photochemical and Thermal Ring-Opening/Closure Reactions and Solvent Dependence in Spirooxazines

2012 ◽  
Vol 116 (31) ◽  
pp. 8148-8158 ◽  
Author(s):  
Pedro J. Castro ◽  
Isabel Gómez ◽  
Maurizio Cossi ◽  
Mar Reguero
Keyword(s):  
Ring Opening ◽  
Computational Study ◽  
Solvent Dependence

scholarly journals Divergent Reactivity of Indole-Tethered Ynones with Silver(I) and Gold(I) Catalysts: A Combined Synthetic and Computational Study

Synthesis ◽  
2018 ◽  
Vol 50 (24) ◽  
pp. 4829-4836 ◽  
Author(s):  
Jason Lynam ◽  
Richard Taylor ◽  
William Unsworth ◽  
John Liddon ◽  
James Rossi-Ashton ◽  
...  
Keyword(s):  
Ring Opening ◽  
Computational Study ◽  
Dft Study ◽  
Migration Mechanism ◽  
Catalyst Systems

A combined synthetic and computational (DFT) study has been performed to account for the divergent reactivity of indole-tethered ynones when treated with Ag(I) and Au(I) catalysts. The two catalyst systems deliver spirocyclic indolenines and carbazoles, respectively, from the same precursors, with the reaction outcomes believed to be a result of differences in the rates of a key protodemetalation step. A ring-opening/ring-closing isomerisation process is proposed to enable the interconversion of spirocyclic and C-2 annulated indole intermediates, in contrast to the 1,2-migration mechanism tentatively proposed in previous studies.

Computational study of the ring opening mechanism of substituted temolozolomide, TMZ-R (R = Cl, OH, CF3) in water solvent

2019 ◽  
Vol 732 ◽  
pp. 136651
Author(s):  
Romain Mavudila ◽  
Jules Tshishimbi Muya ◽  
Chung Hoeil ◽  
Okuma Emile Kasende
Keyword(s):  
Ring Opening ◽  
Computational Study ◽  
Water Solvent

Experimental and Computational Study of the Conrotatory Ring Opening of Various 3-Chloro-2-azetines

2008 ◽  
Vol 73 (14) ◽  
pp. 5481-5488 ◽  
Author(s):  
Sven Mangelinckx ◽  
Veronique Van Speybroeck ◽  
Peter Vansteenkiste ◽  
Michel Waroquier ◽  
Norbert De Kimpe
Keyword(s):  
Ring Opening ◽  
Computational Study

scholarly journals A Computational Study of 2-(chloromethyl)oxirane Ring Opening by Bromide and Acetate Anions Considering Electrophilic Activation with Cations of Alkali Metals

2019 ◽  
Vol 92 (3) ◽  
pp. 357-367 ◽  
Author(s):  
Kseniia Yutilova ◽  
Yuliia Bespal’ko ◽  
Elena Shved
Keyword(s):  
Alkali Metal ◽  
Metal Cation ◽  
Ring Opening ◽  
Density Functional ◽  
Alkali Metals ◽  
Computational Study ◽  
Alkali Metal Cation ◽  
Transition States ◽  
Activation Parameters ◽  
Electrophilic Activation

Ring opening of 2-(chloromethyl)oxirane via the nucleophilic substitution with bromide and acetate anions was investigated using density functional theory (DFT) calculations. It was shown that the geometry of the transition states and the activation parameters of the reactions correspond to those of SN2-like mechanism. The nature of localized transition states was analyzed using More O’Ferrall – Jencks plots. The quantum chemical simulations of the potential energy surface for the ring-opening reaction of oxirane by nucleophiles confirmed the theoretical assumptions about the favored path of interactions, which is a backside α-attack of nucleophile. The effect of alkali metal cation (Li+, Na+, K+) on that path was estimated. It was found that the electrophilic activation with alkali metal cation is more pronounced in the reaction of 2-(chloromethyl)oxirane with dissociated ions, than with ionic pairs.

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