Theoretical Study of Sigmatropic Rearrangement Reaction of Cycloprop-2-EN-1-Amine and Its Fluorine Derivatives

2017 ◽  
Vol 7 (12) ◽  
pp. 1234-1241
Author(s):  
A. Sangeetha ◽  
A. Thaminum Ansari ◽  
Jebakumar Jeevanandam and S. Jayaprakash
Keyword(s):  
Theoretical Study ◽  
Sigmatropic Rearrangement ◽  
Rearrangement Reaction

scholarly journals Theoretical Study of Sigmatropic Rearrangement of Cycloprop-2-en-1-ol and its Fluorine Derivatives: Pericyclic or Pseudopericyclic Character from NICS and LLPE

2019 ◽  
Vol 31 (3) ◽  
pp. 597-601
Author(s):  
A. Sangeetha ◽  
A. Thaminum Ansari ◽  
Jebakumar Jeevanandam ◽  
S. Jayaprakash
Keyword(s):  
Oxygen Atom ◽  
Gas Phase ◽  
Energy Barrier ◽  
Fluorine Atom ◽  
Theoretical Study ◽  
Lone Pair ◽  
Sigmatropic Rearrangement ◽  
Nucleus Independent Chemical Shift ◽  
Lone Pair Electron ◽  
Rearrangement Reaction

Sigmatropic rearrangement reaction of cycloprop-2-en-1-ol and its fluorine derivatives has been studied theoretically in gas phase and its energy barrier has been calculated. Nucleus-independent chemical shift (NICS) shows sigmatropic rearrangement of cycloprop-2-en-1-ol is pericyclic in nature whereas fluorine derivatives show pseudopericyclic and pericyclic nature. Substitution of fluorine atom at ring is found to increase the energy barrier for –OH migration, while substitution at oxygen atom reduces the barrier. To know the involvement of lone pair of electrons during the reaction, lone pair electron present on oxygen atom is locked by hydrogen bonding. CR-CCSD(T)/6-311+G** levels are used to study the reactions more accurately.

scholarly journals Facile One-Pot Synthesis of Benzo[h]isoquinolines via Strong Acid Triggered [1,2]-Sigmatropic Rearrangement: A Theoretical and Experimental Studies

2019 ◽  
Vol 31 (9) ◽  
pp. 2133-2138
Author(s):  
V.M. Boitsov ◽  
N.A. Knyazev ◽  
S.V. Shmakov ◽  
S.Yu. Vyazmin ◽  
D.M. Nikolaev ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Experimental Studies ◽  
Strong Acid ◽  
Sigmatropic Rearrangement ◽  
Biologically Active ◽  
One Pot ◽  
One Pot Synthesis ◽  
Rearrangement Reaction ◽  
Isoquinoline Derivatives

Benzo[h]isoquinoline scaffold is of interest as a rigid subunit that can be useful for constructing biologically active products. However, no good-yielded synthetic pathway to this ring system has been reported yet. Herein, a facile one-pot synthesis from N-aryl itaconimides and 1,3-diarylisobenzofuran via strong acid triggered skeletal rearrangement reaction is described. Theoretical study for this rearrangement is provided at M11/cc-pVDZ level of theory. Antitumor activity of obtained benzo[h]isoquinoline derivatives against human erythroleukemia K562 cell line was evaluated in vitro by MTS-assay.

Catalyst-Free [2,3]-Sigmatropic Rearrangement Reactions of Photochemically Generated Ammonium Ylides

Synthesis ◽  
2019 ◽  
Vol 51 (23) ◽  
pp. 4348-4358 ◽  
Author(s):  
Fang Li ◽  
Feifei He ◽  
Rene M. Koenigs
Keyword(s):  
Visible Light ◽  
Sigmatropic Rearrangement ◽  
Tertiary Amines ◽  
Amino Esters ◽  
Catalyst Free ◽  
Rearrangement Reaction ◽  
Rearrangement Reactions ◽  
Free Ammonium

The rearrangement reaction of ammonium ylides furnishes valuable α,α-disubstituted amino esters. In this work, we describe the visible-light photolysis reaction of aryldiazoacetates in the presence of tertiary amines that react via a free ammonium ylide in a sigmatropic rearrangement reaction to provide amino esters in moderate to very good yields (33 examples, up to 97% yield).

Can a photochemical reaction be concerted? A theoretical study of the photochemical sigmatropic rearrangement of but-1-ene

1992 ◽  
Vol 114 (14) ◽  
pp. 5805-5812 ◽  
Author(s):  
Fernando Bernardi ◽  
Massimo Olivucci ◽  
Michael A. Robb ◽  
Glauco Tonachini
Keyword(s):  
Photochemical Reaction ◽  
Theoretical Study ◽  
Sigmatropic Rearrangement

scholarly journals Isomerization Reactions in Anionic Mesoionic Carbene-Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions

2020 ◽  
Author(s):  
Biprajit Sarkar ◽  
Jessica Stubbe ◽  
Nicolás I. Neuman ◽  
Ross McLellan ◽  
Michael G. Sommer ◽  
...  
Keyword(s):  
Metal Complexes ◽  
Coordination Sphere ◽  
Theoretical Study ◽  
Spin States ◽  
Secondary Coordination Sphere ◽  
Rearrangement Reaction ◽  
And Control

A unique rearrangement reaction is presented for borate containing mesoionic carbenes. The corresponding Co<sup>II</sup> complexes display spin states, coordination geeometries and reactivities that are controlled through aogstic interactions on the secondary coordination sphere. A comprehensive NMR spectroscopic, crystallographic, EPR spectroscopic and theoretical study is presented on the ligands and the metal complexes.<br>

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