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 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.

THEORETICAL STUDY OF PHOTO-PHYSICAL PROCESSES IN 2-ARYL SUBSTITUTED INDOLES

2012 ◽  
Vol 11 (06) ◽  
pp. 1311-1322
Author(s):  
ZILONG ZHENG ◽  
YI ZHAO ◽  
SHINKOH NANBU
Keyword(s):  
Charge Transfer ◽  
Ab Initio ◽  
Photochemical Reaction ◽  
Theoretical Study ◽  
Intramolecular Charge Transfer ◽  
Ab Initio Method ◽  
Physical Processes ◽  
Strong Fluorescence ◽  
Neutral Compounds ◽  
Linear Reaction

Ab initio method is used to figure out the structures and photo-physical processes of 2-aryl substituted indoles, 2-phenylindole (2PI), 2-naphthylindole (2NI), and 2-anthracenylindole (2AI), synthesized experimentally with strong fluorescence. The results show that the photoabsorption and fluorescence measured experimentally correspond to the monovalent anions deprotonated in the indole NH end, other than the neutral compounds. During the photochemical reaction, the angles between the planes of the indole and 2-aryl substituted moieties keep unchanged, but the photo-induced intramolecular charge transfer can immediately occur in the anions. Furthermore, the photo-physical processes after photoexcitation are analyzed by using a linear reaction coordinate.

scholarly journals An MO Theoretical Study of the Photochemical Reaction of Alkanenitronate Anions to Form Hydroxamic Acids

1982 ◽  
Vol 55 (5) ◽  
pp. 1509-1513 ◽  
Author(s):  
Osamu Kikuchi ◽  
Takazumi Kanekiyo ◽  
Seiji Tanaka ◽  
Kiyoshi Naruchi ◽  
Kazutoshi Yamada
Keyword(s):  
Photochemical Reaction ◽  
Theoretical Study ◽  
Hydroxamic Acids

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
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