Unveiling the Chemistry of Higher-Order Cycloaddition Reactions within the Molecular Electron Density Theory by Luis R. Domingo Mar Ríos-Gutiérrez & Patricia Pérez
Author:Luis R. Domingo, Mar Ríos-Gutiérrez & Patricia Pérez
Format: pdf
Tags: The higher-order cycloaddition (HOCA) reaction of tropone with cyclopentadiene (Cp) has been studied within the Molecular Electron Density Theory. The Electron Localization Function (ELF) analysis of the electronic structure of tropone and Cp characterizes the structural behaviors of the two conjugated unsaturated systems, while the conceptual DFT reactivity indices classify tropone as a strong electrophile and Cp as a strong nucleophile participating in polar cycloaddition reactions of reverse electron density flux. Eight competitive reaction paths have been characterized for this cycloaddition reaction. The most favorable one allowing the formation of the formal out [6 + 4] cycloadduct has an activation enthalpy of 16.2 kcalmol-1, and the reaction is exothermic by -21.4 kcalmol-1. This HOCA reaction, which takes place through a non-concerted two-stage one-step mechanism, presents high stereo-, pseudocyclic- and regioselectivities, explaining the exclusive formation of the experimental [6 + 4] cycloadduct. While the most favorable nucleophilic attack of Cp on most electrophilic C2 positions of tropone accounts for regioselectivities, the favorable electrostatic interactions present between the Cp framework and the negatively charged O8 oxygen of tropone account for the stereo- and pseudocyclic selectivities. Despite the symmetry of the two reagents, this HOCA reaction takes place via a highly asynchronous transition state structure as a consequence of the most favorable two-center interactions taking place between the electrophilic C2 center of tropone and the nucleophilic C9 center of Cp., higher-order cycloaddition reactions; molecular electron density theory; molecular mechanism; tropone; selectivity
Download
This site does not store any files on its server. We only index and link to content provided by other sites. Please contact the content providers to delete copyright contents if any and email us, we'll remove relevant links or contents immediately.
Alchemy and Alchemists by C. J. S. Thompson(3280)
The Elements by Theodore Gray(2831)
The Club by A.L. Brooks(2734)
How to Make Your Own Soap by Sally Hornsey(2725)
Drugs Unlimited by Mike Power(2475)
Wheels of Life by Anodea Judith(1890)
Cracking the Sat French Subject Test, 2013-2014 Edition by The Princeton Review(1735)
Perfume by Jean-Claude Ellena(1726)
The Flavor Matrix by James Briscione(1698)
The Cosmic Machine: The Science That Runs Our Universe and the Story Behind It by Scott Bembenek(1685)
Cracking the LSAT, 2012 Edition by Princeton Review(1658)
1000 Multiple-Choice Questions in Organic Chemistry by Organic Chemistry Academy(1562)
MCAT Physics and Math Review by Princeton Review(1553)
Cracking the SAT Premium Edition with 6 Practice Tests, 2017 by Princeton Review(1466)
Handbook of Modern Sensors by Jacob Fraden(1464)
A is for Arsenic: The Poisons of Agatha Christie (Bloomsbury Sigma) by Kathryn Harkup(1447)
The Thing Around Your Neck by Chimamanda Ngozi Adichie(1441)
Synchrotron Light Sources and Free-Electron Lasers by Eberhard J. Jaeschke Shaukat Khan Jochen R. Schneider & Jerome B. Hastings(1440)
Harry Potter All Books: 8 Books by J.k.rowling(1421)
