Structure Correlation Study of Some Diels–Alder Cycloadducts of Anthracene

2009 ◽  
Vol 62 (5) ◽  
pp. 419 ◽  
Author(s):  
Yit W. Goh ◽  
Jonathan M. White
Keyword(s):  
Correlation Study ◽  
Alder Reaction ◽  
Diels Alder ◽  
Ground State Structure ◽  
State Structure ◽  
Structural Effects ◽  
Early Stages ◽  
Diels Alder Reaction ◽  
Structure Correlation ◽  
Qualitative Relationship

Crystal structures of some Diels–Alder cycloadducts of anthracene and a variety of dienophiles reveal structural effects consistent with the manifestation of the early stages of the retro Diels–Alder reaction in the ground state structure. The symmetrical cycloadducts 3 and 4 reveal a qualitative relationship between structure and reactivity, whereas the cycloadducts of 9-methoxyanthracene show structural effects suggestive of the early stages of an asynchronous retro Diels–Alder reaction.

Structural Studies on α-Pyrone Cycloadducts. Manifestation of the Early Stages of CO2 Extrusion by retro Hetero-Diels - Alder Reaction

2009 ◽  
Vol 62 (5) ◽  
pp. 407 ◽  
Author(s):  
Jesse Roth-Barton ◽  
Yit Wooi Goh ◽  
Asimo Karnezis ◽  
Jonathan M. White
Keyword(s):  
Normal Values ◽  
Alder Reaction ◽  
Diels Alder ◽  
Structural Studies ◽  
State Structure ◽  
Transition State Structure ◽  
Early Stages ◽  
Diels Alder Reaction ◽  
Decarboxylation Reaction ◽  
Ground State Structures

Structures of the α-pyrone (pyran-2-one) cycloadducts 4–8 show deviations of some bond distances from their normal values, consistent with manifestation of the early stages of the retro hetero-Diels–Alder decarboxylation reaction in the ground state structures. Thus the bridgehead C–O(CO) and C–CO(O) bonds are lengthened and the bridging C–O bond is shortened. The degree of lengthening of the C–O(CO) and C–CO(O) bonds is similar, whereas in the calculated transition state structure there is significant asymmetry in the extent of C–CO(O) and C–O(CO) bond breaking.

scholarly journals Applying the Structure Correlation Principle to retro Diels Alder Reactions

2014 ◽  
Vol 70 (a1) ◽  
pp. C923-C923
Author(s):  
Brett Pool ◽  
Rachel Goh ◽  
Jesse Roth-Barton ◽  
Jonathan White
Keyword(s):  
Ground State ◽  
Alder Reaction ◽  
Diels Alder ◽  
Frontier Orbitals ◽  
X Ray ◽  
Diels Alder Reaction ◽  
Transition State Geometry ◽  
Standard Values ◽  
Structure Correlation ◽  
Fragmentation Reactions

The early stages of molecular rearrangements are often apparent in the crystal structures of molecules susceptible to that rearrangement. For example, if a particular bond is broken, or if a particular group migrates during the rearrangement, then deviations of bond distances and angles from their `standard values' along the reaction coordinate are often observed. This is the structure correlation principle,1 which holds provided the molecule exists in the ground state, in a geometry, which is similar to the transition state geometry for the reaction. In this geometry the frontier orbitals whose interactions facilitate the reaction, can mix in the ground state. This paper discusses the application of this principle to pericyclic fragmentation reactions related to the retro Diels Alder reaction, using low temperature X-ray structural analysis of a range of model substrates. The substrates can be classified on the basis of this data into three groups: (i) those that undergo a synchronous retro Diels Alder reaction, (2) those that undergo an asynchronous retro Diels Alder reaction, and (3) those that react via a 2-step process. Examples of molecules falling into these three categories are given below.

ChemInform Abstract: Structural Effects Controlling the Rate of the Retro-Diels-Alder Reaction in Anthracene Cycloadducts.

ChemInform ◽  
1989 ◽  
Vol 20 (34) ◽  
Author(s):  
Y. CHUNG ◽  
B. F. DUERR ◽  
T. A. MCKELVEY ◽  
P. NANJAPPAN ◽  
A. W. CZARNIK
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
Structural Effects ◽  
Diels Alder Reaction

Structural effects controlling the rate of the retro-Diels-Alder reaction in anthracene cycloadducts

1989 ◽  
Vol 54 (5) ◽  
pp. 1018-1032 ◽  
Author(s):  
Yongseog Chung ◽  
Brook F. Duerr ◽  
Timothy A. McKelvey ◽  
P. Nanjappan ◽  
Anthony W. Czarnik
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
Structural Effects ◽  
Diels Alder Reaction

The Diels-Alder Reaction of 2-Ethenyl-1,4-Benzodioxin: A New and Simple Synthesis of Bisaryl Ethers

Synlett ◽  
1989 ◽  
Vol 1989 (01) ◽  
pp. 30-32
Author(s):  
Thomas V. Lee ◽  
Alistair J. Leigh ◽  
Christopher B. Chapleo
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
Simple Synthesis ◽  
Diels Alder Reaction
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