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10.01 Bicyclic 5-5 Systems: Two Heteroatoms 1:1 ˇ ´kova´ A. Krutosı University of St. Cyril and Methodius, Trnava, Slovakia T. Gracza Slovak University of Technology, Bratislava, Slovakia ª 2008 Elsevier Ltd. All rights reserved. 10.01.1
Introduction
2
10.01.2
Theoretical Methods
5
10.01.3
Experimental Structural Methods
5
10.01.3.1
X-Ray Diffraction Studies
5
10.01.3.2
Proton NMR Spectroscopy
6
10.01.3.3
Carbon-13 NMR Spectroscopy
6
10.01.3.4
Nitrogen-15 NMR Spectroscopy
7
10.01.3.5
Polarography
8
10.01.3.6
UV Spectroscopy
9
10.01.3.7
Photoelectron Spectrometry
9
10.01.4 10.01.4.1 10.01.5 10.01.5.1
Thermodynamic Aspects
11
1,4-Diheteropentalene Systems (1)
11
Electrophilic attack at carbon Electrophilic attack at nitrogen Electrophilic attack at sulfur Ring-opening reactions Cycloaddition reactions
11 13 14 15 15
1,5-Diheteropentalene Systems (2)
16
10.01.5.2.1 10.01.5.2.2
10.01.5.3
16 19
20
Electrophilic attack at carbon Enzyme catalyzed attack at carbon Electrophilic attack at nitrogen Electrophilic attack at sulfur Addition and cycloaddition reactions
20 20 20 21 21
2,5-Diheteropentalene Systems (4)
10.01.5.4.1 10.01.5.4.2
10.01.6
Addition and cycloaddition reactions Radical reactions
1,6-Diheteropentalene Systems (3)
10.01.5.3.1 10.01.5.3.2 10.01.5.3.3 10.01.5.3.4 10.01.5.3.5
10.01.5.4
9
Reactivity of Fully Conjugated Rings
10.01.5.1.1 10.01.5.1.2 10.01.5.1.3 10.01.5.1.4 10.01.5.1.5
10.01.5.2
9
Aromaticity
21
Cycloaddition reactions Other Reactions
22 23
Reactivity of Nonconjugated Rings
23
10.01.6.1
1,4-Diheteropentalene Systems
23
10.01.6.2
1,5-Diheteropentalene Systems
24
10.01.6.3
1,6-Diheteropentalene Systems
25
10.01.6.4
2,5-Diheteropentalene Systems
25
10.01.7 10.01.7.1
Reactivity of Substituents Attached to Ring Carbon Atoms 1,4-Diheteropentalene Systems
25 25
1
2
Bicyclic 5-5 Systems: Two Heteroatoms 1:1
10.01.7.1.1 10.01.7.1.2
10.01.7.2
1,6-Diheteropentalene Systems
10.01.7.2.1 10.01.7.2.2 10.01.7.2.3
10.01.8 10.01.8.1 10.01.9 10.01.9.1
1,4-Diheteropentalene Systems Ring Syntheses Syntheses of 1,4-Diheteropentalene Systems (1)
Synthesis by construction of the second heterocyclic ring onto an existing heterocycle
Syntheses of 1,6-Diheteropentalene Systems (3)
10.01.9.3.1
10.01.9.4
Synthesis by construction of the second heterocyclic ring onto an existing heterocycle
Syntheses of 1,5-Diheteropentalene Systems (2)
10.01.9.2.1
10.01.9.3
Carboxylic acids and derivatives Aldehydes Halogen substituents
Reactivity of Substituents Attached to Ring Heteroatoms
10.01.9.1.1
10.01.9.2
Carboxylic acids and derivatives Aldehydes
Synthesis by construction of the second heterocyclic ring onto an existing heterocycle
Syntheses of 2,5-Diheteropentalene Systems (4)
10.01.9.4.1 10.01.9.4.2
Synthesis by construction of the second heterocyclic ring onto an existing heterocycle Other systems
25 30
32 32 33 36
37 37 39 39 39
42 42
50 50
52 52 55
10.01.10
Ring Syntheses by Transformati