Stereoelectronic effects: a bridge between structure and reactivity
Gespeichert in:
| 1. Verfasser: | |
|---|---|
| Format: | Buch |
| Sprache: | English |
| Veröffentlicht: |
Chichester, West Sussex
Wiley
[2016]
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| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis |
| Beschreibung: | viii, 381 Seiten Illustrationen, Diagramme |
| ISBN: | 9781118906347 |
Internformat
MARC
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| 100 | 1 | |a Alabugin, Igor V. |e Verfasser |0 (DE-588)1117169774 |4 aut | |
| 245 | 1 | 0 | |a Stereoelectronic effects |b a bridge between structure and reactivity |c Igor V. Alabugin, Department of Chemistry and Biochemistry, Florida State University, USA |
| 264 | 1 | |a Chichester, West Sussex |b Wiley |c [2016] | |
| 300 | |a viii, 381 Seiten |b Illustrationen, Diagramme | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 650 | 4 | |a Stereochemistry | |
| 650 | 4 | |a Reactivity (Chemistry) | |
| 650 | 4 | |a Molecular structure | |
| 650 | 0 | 7 | |a Stereoelektronischer Effekt |0 (DE-588)4402676-6 |2 gnd |9 rswk-swf |
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Datensatz im Suchindex
| _version_ | 1804176696113364992 |
|---|---|
| adam_text | Contents
Q-
Acknowledgement ix
Supplementary Material x
1 Introduction 1
1.1 Stereoelectronic effects - orbital interactions in control of structure and reactivity 1
1.2 Orbital interactions in theoretical chemistry 3
1.3 The birth of stereoelectronic concepts in organic chemistry 4
References 6
2 Direct Effects of Orbital Overlap on Reactivity 8
2.1 Bond formation without bond breaking: types of overlap in two-orbital interactions 9
2.1.1 Factors controlling o-bond overlap 12
2.2 Bond formation coupled with bond breaking 25
2.2.1 Three-orbital interactions: stereoelectronic reasons for the preferred trajectories
of intermolecular attack at a chemical bond 25
2.3 Stereoelectronics of supramolecular interactions 29
2.3.1 FMO interactions in intermolecular complexes 29
2.3.2 Expanding the palette of supramolecular interactions: from H-bonding to Li-,
halogen, pnictogen, chalcogen and tetrel binding 30
References 36
3 Beyond Orbital Overlap: Additional Factors Important for Orbital Interactions.
Classifying Delocalizing Interactions 42
3.1 Electronic count: two-electron, one-electron and three-electron bonds 43
3.2 Iso valent vs. sacrificial conjugation 48
3.3 Neutral, negative, and positive hyperconjugation 49
References 52
4 Computational and Theoretical Approaches for Studies of Stereoelectronic Effects 54
4.1 Quantifying orbital interactions 54
4.2 Localized orbitals from delocalized wavefunctions 56
References 60
62
62
63
64
65
68
68
68
81
84
91
92
92
97
99
99
105
110
113
114
117
121
122
122
124
124
126
129
142
143
147
147
157
167
168
170
183
184
184
Contents
General Stereoelectronic Trends - Donors, Acceptors, and Chameleons
5.1 Three types of delocalization: conjugation, hyperconjugation, and c-conjugation
5.2 Geminal and vicinal interactions
5.3 Stereoelectronic main rule: antiperiplanarity
5.3.1 Effects of bond polarity
5.3.2 Polarity-induced acceptor anisotropy
5.4 Scales of donor and acceptor ability of orbitals: polarization, hybridization,
and orbital energy effects
5.4.1 Donors
5.4.2 Acceptors
5.4.3 Stereoelectronic chameleons: donors masquerading as acceptors
5.5 Cooperativity of stereoelectronic effects and antiperiplanar lone pair hypothesis (ALPH)
theory - several donors working together
5.6 Summary
References
Stereoelectronic Effects with Donor and Acceptor Separated by a Single
Bond Bridge: The Broad Spectrum of Orbital Contributions to
Conformational Analysis
6.1 c/a-Interactions
6.1.1 Rotational barrier in ethane
6.1.2 Axial/equatorial equilibrium in methylcyclohexane
6.1.3 The gauche effect
6.2 a/?:-Interactions
6.2.1 “Eclipsed” and “staggered” conformations of alkenes - stereoelectronic
misnomers
6.2.2 Carbonyls
6.2.3 Strained bonds
6.3 p/a-Interactions
6.3.1 Primary, secondary, tertiary carbocation stabilization
6.3.2 Hyperconjomers of cyclohexyl cations
6.3.3 (¡-Silicon effect and related p-effects
6.4 n/o-Interactions
6.4.1 Anomeric effects
6.4.2 Reverse anomeric effect
6.4.3 “Anomeric effects without lone pairs”: beyond the n -* o* interactions
6.5 n/jr-Interactions
6.5.1 Esters and related carboxylic acid derivatives
6.5.2 Vinyl ethers and enamines
6.6 ji/ji-lnteractions
6.6.1 Hyperconjugation in alkynes and its relation to the “absence” of conjugation
between two triple bonds in 1,3-diynes
References
Stereoelectronic Effects with Donor and Acceptor Separated by a Vinyl Bridge
7.1 c/ct* interactions
7.1.1 CE-elTect: the case of two o-acceptors
Contents vii
7.2 o/k interactions: allenes vs. alkenes 185
7.2.1 Neutral systems 185
7.2.2 Anions 186
7.2.3 Positive conjugation and hyperconjugation in vinyl systems 187
7.2.4 a jc* delocalization in allenes: allenyl silanes in reactions
with electrophiles 188
7.3 Vinyl halides and their carbanions (transition from gc H-+ o*CHal to nc-► a*c Ha] interactions) 192
7.3.1 Heteroatom-containing systems 195
7.4 Diazenes and the isomerization of azo compounds 196
7.5 Antiperiplanarity in coordinated bond-breaking and bond-forming processes:
eliminations, fragmentations and additions 199
7.6 Syn-periplanarity: the second best choice 207
References 208
8 Remote Stereoelectronic Effects 214
8.1 Extended through space interactions: homoconjugation and homohyperconjugation 215
8.1.1 Homoconjugation 215
8.1.2 Homoanomeric effects 217
8.1.3 Cross-hyperconjugation 223
8.2 Double hyperconjugation and through-bond interactions 223
8.3 Combined through-bond and through-space interactions 228
8.4 Symmetry and cooperativity effects in cyclic structures 229
8.4.1 Hyperaromaticity 229
8.4.2 o-Aromaticity 230
8.4.3 Double aromaticity 231
References 231
9 Transition State Stabilization with Stereoelectronic Effects: Stereoelectronic
Control of Reaction Bottlenecks 236
9.1 Torquoselectivity 240
9.2 Diastereoselection in nucleophilic addition to carbonyl compounds
and other rc-systems 243
9.3 Electrophilic addition to enamines 245
9.4 Hyperconjugative assistance to alkyne bending and alkyne cycloadditions 246
9.5 Negative conjugation - donation from oxygen lone pairs to breaking bonds 248
9.6 Remote lone pairs in radical reactions: fragmentations 251
References 254
10 Stereoelectronic Effects in Reaction Design 257
10.1 Static stereoelectronics 257
10.2 Dynamic stereoelectronics 259
References 273
11 Stereoelectronic Effects in Action: The Many Doors Opened by
Orbital Interactions 275
11.1 Gauche effect (o -► o* interactions) 275
11.2 Trans-effect - the cousin of gauche effect in organometallic chemistry 283
viii Contents
11.3 Anomeric effects (n o* interactions) 284
11.3.1 Cooperativity and anticooperativity in anomeric systems 288
11.3.2 Spectrum of armed and disarmed glycosides 289
11.3.3 Restoring exo-anomeric effect in carbasugars 294
11A Bioorganic chemistry and enzyme reactions 311
References 316
12 Probing Stereoelectronic Effects with Spectroscopic Methods 322
12.1 infrared spectroscopy 323
12.1.1 Bohlmann effect 323
12.1.2 Red-shifting hydrogen bonds - an intermolecular version of the
Bohlmann effect 331
12.2 Nuclear magnetic resonance spectroscopy 335
12.2.1 Stereoelectronic effects on chemical shifts 335
12.2.2 Diamagnetic effects in lH NMR 336
12.2.3 Paramagnetic effects in 13C NMR 338
12.2.4 Through-space interactions - y-substituent effects 340
12.2.5 Stereoelectronic effects on coupling constants 342
12.3 Conclusion 368
References 368
Index 376
|
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| spelling | Alabugin, Igor V. Verfasser (DE-588)1117169774 aut Stereoelectronic effects a bridge between structure and reactivity Igor V. Alabugin, Department of Chemistry and Biochemistry, Florida State University, USA Chichester, West Sussex Wiley [2016] viii, 381 Seiten Illustrationen, Diagramme txt rdacontent n rdamedia nc rdacarrier Stereochemistry Reactivity (Chemistry) Molecular structure Stereoelektronischer Effekt (DE-588)4402676-6 gnd rswk-swf Stereoelektronischer Effekt (DE-588)4402676-6 s DE-604 Erscheint auch als Online-Ausgabe, ePUB 978-1-118-90636-1 Digitalisierung UB Bayreuth - ADAM Catalogue Enrichment application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=029243075&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Alabugin, Igor V. Stereoelectronic effects a bridge between structure and reactivity Stereochemistry Reactivity (Chemistry) Molecular structure Stereoelektronischer Effekt (DE-588)4402676-6 gnd |
| subject_GND | (DE-588)4402676-6 |
| title | Stereoelectronic effects a bridge between structure and reactivity |
| title_auth | Stereoelectronic effects a bridge between structure and reactivity |
| title_exact_search | Stereoelectronic effects a bridge between structure and reactivity |
| title_full | Stereoelectronic effects a bridge between structure and reactivity Igor V. Alabugin, Department of Chemistry and Biochemistry, Florida State University, USA |
| title_fullStr | Stereoelectronic effects a bridge between structure and reactivity Igor V. Alabugin, Department of Chemistry and Biochemistry, Florida State University, USA |
| title_full_unstemmed | Stereoelectronic effects a bridge between structure and reactivity Igor V. Alabugin, Department of Chemistry and Biochemistry, Florida State University, USA |
| title_short | Stereoelectronic effects |
| title_sort | stereoelectronic effects a bridge between structure and reactivity |
| title_sub | a bridge between structure and reactivity |
| topic | Stereochemistry Reactivity (Chemistry) Molecular structure Stereoelektronischer Effekt (DE-588)4402676-6 gnd |
| topic_facet | Stereochemistry Reactivity (Chemistry) Molecular structure Stereoelektronischer Effekt |
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