Transition states in catalyzed and uncatalyzed Diels-Alder reactions. Cooperativity as a probe of geometry

1984 ◽  
Vol 106 (13) ◽  
pp. 3806-3810 ◽  
Author(s):  
Laren M. Tolbert ◽  
Mahfuza B. Ali
Keyword(s):  
Transition States ◽  
Diels Alder

Systematic Comparisons between Broken Symmetry and Symmetry-Adapted Approaches to Transition States by Chemical Indices:  A Case Study of the Diels−Alder Reactions†

2003 ◽  
Vol 107 (5) ◽  
pp. 682-694 ◽  
Author(s):  
Hiroshi Isobe ◽  
Yu Takano ◽  
Yasutaka Kitagawa ◽  
Takashi Kawakami ◽  
Syusuke Yamanaka ◽  
...  
Keyword(s):  
Transition States ◽  
Diels Alder ◽  
Broken Symmetry

scholarly journals Dynamics, transition states, and timing of bond formation in Diels-Alder reactions

2012 ◽  
Vol 109 (32) ◽  
pp. 12860-12865 ◽  
Author(s):  
K. Black ◽  
P. Liu ◽  
L. Xu ◽  
C. Doubleday ◽  
K. N. Houk
Keyword(s):  
Bond Formation ◽  
Transition States ◽  
Diels Alder

scholarly journals Hydrogen bond stabilization in Diels–Alder transition states: The cycloaddition of hydroxy-ortho-quinodimethane with fumaric acid and dimethylfumarate

2005 ◽  
Vol 406 (4-6) ◽  
pp. 355-359 ◽  
Author(s):  
V. Tamilmani ◽  
C.A. Daul ◽  
J. Lage Robles ◽  
C.G. Bochet ◽  
P. Venuvanalingam
Keyword(s):  
Hydrogen Bond ◽  
Fumaric Acid ◽  
Transition States ◽  
Diels Alder

Enhanced Hydrogen Bonding of Water to Diels-Alder Transition States. Ab Initio Evidence

1994 ◽  
Vol 59 (4) ◽  
pp. 803-805 ◽  
Author(s):  
James F. Blake ◽  
Dongchul Lim ◽  
William L. Jorgensen
Keyword(s):  
Hydrogen Bonding ◽  
Ab Initio ◽  
Transition States ◽  
Diels Alder

Organic transition states. V. The Diels-Alder reaction

1976 ◽  
Vol 98 (8) ◽  
pp. 2190-2198 ◽  
Author(s):  
R. E. Townshend ◽  
G. Ramunni ◽  
G. Segal ◽  
W. J. Hehre ◽  
L. Salem
Keyword(s):  
Transition States ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction ◽  
Organic Transition

QTAIM–DI–VISAB computational study on the Diels–Alder reaction of cyclopentadiene — On the nature of the so-called secondary orbital interactions

2008 ◽  
Vol 86 (7) ◽  
pp. 737-744 ◽  
Author(s):  
Nick Henry Werstiuk ◽  
Wojciech Sokol
Keyword(s):  
Computational Study ◽  
Transition States ◽  
Alder Reaction ◽  
Diels Alder ◽  
Physical Organic Chemistry ◽  
Hydrogen Atoms ◽  
Endo Isomer ◽  
Orbital Interactions ◽  
Physical Organic ◽  
Diels Alder Reaction

We have undertaken a QTAIM–DI–VISAB computational study of the dimerization of cyclopentadiene (1), the archetypal example of a Diels–Alder reaction that has been studied experimentally and computationally. Secondary orbital interactions (SOIs) that have gained acceptance in the interpretation of stereoselectivities seen in many cycloaddition reactions have been used to account for the fact that the endo isomer was the kinetic product of the reaction. To this point, “classical” MO analyses along with a variety of arbitrarily assigned solid and dashed lines (solid lines and bold dashes for “primary” interactions and dashed and dotted lines to differentiate between different SOI schemes) have been used in an attempt to describe the bonding of the transition states. Yet, the existence of SOIs has been challenged. Our interest in applying QTAIM to fundamental chemical problems in physical organic chemistry, with the goal of refining our knowledge of the bonding in transition-states and ground-state molecules while obviating the need to use a variety of confusing arbitrarily assigned dashed and dotted lines, led us to a QTAIM–DI–VISAB computational study of the endo and exo dimerizations of 1 at the DFT B3PW91 and MPW1PW91 levels. We have characterized the bonding interactions between cyclopentadiene rings in the various transition states and show that “normal” bonds are present where SOIs have been considered to exist. There is no need to use different types of dashed and dotted lines. An analysis of the changes in atom energies revealed that the significant destabilization of the carbon atoms in achieving the TSs (potentially leading to a very high barrier) is ameliorated by a stabilization of the hydrogen atoms leading to the relatively low barrier for the D–A reaction.Key words: cyclopentadiene dimerization, bispericyclic transition states, DFT calculations, QTAIM–DI–VISAB analysis, bonding, atom energy analysis.

ChemInform Abstract: ORGANIC TRANSITION STATES. V. THE DIELS-ALDER REACTION

1976 ◽  
Vol 7 (27) ◽  
pp. no-no
Author(s):  
R. E. TOWNSHEND ◽  
G. RAMUNNI ◽  
G. SEGAL ◽  
W. J. HEHRE ◽  
L. SALEM
Keyword(s):  
Transition States ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction ◽  
Organic Transition

Ambimodal Transition States in Diels−Alder Cycloadditions of Tropolone and Tropolonate with N‐Methylmaleimide

2021 ◽  
Author(s):  
Kendall N. Houk ◽  
Hong Zhang ◽  
Mathias Kirk Thøgersen ◽  
Cooper S. Jamieson ◽  
Xiao-Song Xue ◽  
...  
Keyword(s):  
Transition States ◽  
Diels Alder
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