A Caveat Concerning Anionic Oxy-cope Rearrangements Within Bicyclo[2.2.2]octenyl Frameworks

Compounds (10), (15) and (16) all react with potassium hydride at 0°C to give, via retro- Diels-Alder reaction, 1-methylnaphthalene (12) in 60-67% yield. No evidence could be obtained for the formation of a product derived from the anionic oxy-Cope rearrangement of substrate (16).

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Synthesis of Complex Hexacyclic Compounds via a Tandem Rh(II)-Catalyzed Double-Cyclopropanation/Cope Rearrangement/Diels–Alder Reaction

Organic Letters ◽

10.1021/ol502257d ◽

2014 ◽

Vol 16 (18) ◽

pp. 4794-4797 ◽

Cited By ~ 14

Author(s):

Jillian E. Spangler ◽

Yajing Lian ◽

Sandeep N. Raikar ◽

Huw M. L. Davies

Keyword(s):

Alder Reaction ◽

Diels Alder ◽

Cope Rearrangement ◽

Diels Alder Reaction

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The Pressure Effect in Pericyclic Rearrangements: the Cope Rearrangement, Electrocyclization, and the Intramolecular Diels-Alder Reaction

Angewandte Chemie International Edition in English ◽

10.1002/anie.199410791 ◽

1994 ◽

Vol 33 (10) ◽

pp. 1079-1081 ◽

Cited By ~ 22

Author(s):

Matthias K. Diedrich ◽

Dirk Hochstrate ◽

Frank-Gerrit Klärner ◽

Bernd Zimny

Keyword(s):

Pressure Effect ◽

Alder Reaction ◽

Diels Alder ◽

Cope Rearrangement ◽

Diels Alder Reaction

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ChemInform Abstract: Enantioselective Synthesis of 1-Nitrotricyclo[5,2,2,02,6]undeca-3,8-dienes via Tandem Consecutive Asymmetric Diels-Alder Reaction-Cope Rearrangement.

ChemInform ◽

10.1002/chin.199828122 ◽

2010 ◽

Vol 29 (28) ◽

pp. no-no

Author(s):

E. ROMAN ◽

M. BANOS ◽

F. J. HIGES ◽

J. A. SERRANO

Keyword(s):

Alder Reaction ◽

Diels Alder ◽

Enantioselective Synthesis ◽

Cope Rearrangement ◽

Diels Alder Reaction

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Regiochemical aspects of Diels-Alder reactions of cyclopentadienone

Australian Journal of Chemistry ◽

10.1071/ch9772307 ◽

1977 ◽

Vol 30 (10) ◽

pp. 2307 ◽

Cited By ~ 4

Author(s):

MN Paddon-Row ◽

HK Patney ◽

RN Warrener

Keyword(s):

Kinetic Parameters ◽

Transition States ◽

Alder Reaction ◽

Diels Alder ◽

Cope Rearrangement ◽

Diels Alder Reaction ◽

Tentative Explanation

The regiochemistry of the Diels-Alder reaction between cyclopentadienone and 6,6-dimethylfulvene (isopropylidenecyclopentadiene) has been studied. Two adducts (in addition to cyclopentadienone dimer) were isolated and their structures were shown to be endo-10-isopropylidenetricyclo[5,2,1,02,6]-deca-4,8- dien-3-one (6a) and endo-3-isopropylidenetricyclo[5,2,1,02,6]deca-4,8- dien-10-one (7a). Kinetic parameters for the Cope rearrangement (6a) ↔ (7a) have been determined. The adducts (6a) and (7a) were formed in the ratio 45 : 55 respectively. Thus, in contrast to FMO predictions, and to its reaction with cyclopentadiene, cyclopentadienone tends to behave as a diene towards the fulvene. A tentative explanation of these results, based on angle strain in the transition states for the formation of Diels-Alder adducts, is proposed.

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