Oleg G. Kulinkovich

Cyclopropanes in Organic Synthesis (eBook, ePUB)

• Format: ePub

Produktbeschreibung

This is a practical guidebook about cyclopropanes that thoroughly surveys derivatives and transformations, synthetic methods, and experimental efficiency as a gateway for further research and development in the field. Provides comprehensive lists and synthetically-oriented synopses of cyclopropane chemistry review references along with publication data on applications in the syntheses of natural and related biologically active compounds Acts as a resource to help readers better understand cyclopropane applications for the efficient realization of synthetically important organic transformations and popular experimental procedures Includes new developments and up-to-date information that will lead to original methodologies for complex organic synthesis Stresses universality, flexibility, and experimental efficiency of a strategy based on preparing cyclopropane derivatives and performing ring cleavage reactions with inexpensive reagents Focuses on the synthetic potential of cyclopropane applications, for example the synthesis of natural compounds and other target-oriented syntheses via cyclopropane intermediaries, as well on their planning by retrosynthetic analysis

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Produktdetails

• Verlag: John Wiley & Sons
• Seitenzahl: 432
• Erscheinungstermin: 6. Oktober 2015
• Englisch
• ISBN-13: 9781118978412
• Artikelnr.: 43979207

Autorenporträt

Oleg Kulinkovich was the head of the Department of Organic Chemistry from 1993-2003 and the head of the Laboratory of Organoelement Synthesis at Belarusian State University and visiting professor at Tallinn University of Technology. His seminal work on titanium-catalyzed cyclopropanation of carboxylic esters with Grignard reagents bearing beta-hydrogen atoms (Kulinkovich reaction) is very well-known. Dr. Kulinkovich has published several reviews and original articles on organic synthesis in leading international journals.

Inhaltsangabe

Preface ix Part I Reactivity and availability 1 Introduction
1 Reference
2 1 Structure and Reactivity of the Cyclopropane Species 3 1.1 Geometry and Bonding
3 1.2 Energy
4 1.3 Spectra
5 1.4 Cyclopropyl Cations
5 1.5 Cyclopropyl Anions
6 1.6 Cyclopropyl Radicals
7 1.7 Cyclopropylidenes
7 1.8 Cyclopropylcarbinyl Cations
8 1.9 Cyclopropylcarbinyl Anions
8 1.10 Cyclopropylcarbinyl Radicals
10 1.11 Cyclopropylcarbenes
10 1.12 Conclusion
11 References
13 2 Ring Cleavage Reactions 15 2.1 Cyclopropyl Activation
16 2.1.1 Halogen
Oxy
and Sulfur Substituted Cyclopropanes
16 2.1.2 Alkylidenecyclopropanes
19 2.2 Cyclopropylcarbinyl Activation
23 2.2.1 Halogeno
Oxy
Acyl and Metallomethyl Cyclopropanes
23 2.2.2 Alkylidenecyclopropanes
27 2.2.3 Vinyl and Ethynyl Cyclopropanes
29 2.2.4 1
2?]Divinylcyclopropanes
33 2.2.5 Acceptor Cyclopropanes
35 2.2.6 Donor Cyclopropanes
38 2.2.7 Donor-Acceptor Cyclopropanes
43 2.3 Conclusion
48 References
49 3 Synthesis of Cyclopropanes 57 3.1 1
3?]Cyclization Reactions
57 3.1.1 Cyclizations with Cleavage of Two Single Bonds
58 3.1.2 Cyclizations with Cleavage of One Double Bond and One Single Bond
59 3.1.3 Cyclizations with Cleavage of Two Double Bonds
62 3.2 [2 + 1] Cyclization Reactions
65 3.2.1 Cycloaddition of Carbene Equivalents to Olefins
66 3.2.2 Coupling of 1
1?]Carbodianion and 1
2?]Carbodication Equivalents
79 3.2.3 Coupling of 1
1?]Carbodication and 1
2?]Carbodianion Equivalents
83 3.3 Addition Reactions to the Double Bond of Cyclopropenes
88 3.4 Interconversion of Cyclopropanes
90 3.5 Conclusion
90 References
90 Part Ii Synthetic Application 99 Introduction
99 References
100 4 Triangulation Retrosynthetic Analysis 103 4.1 Retrosynthetic Triangulation
103 4.2 Conclusion
108 References
108 5 Acyclic Compounds 109 5.1 Formation of Carbon Substituents
109 5.1.1 Nonactivated Cyclopropane Precursors
109 5.1.2 Cyclopropylcarbinyl Activated Precursors
112 5.1.3 Cooperatively Activated Precursors
138 5.2 Formation of Olefin Groups
139 5.2.1 Cyclopropylcarbinyl Activated Precursors
139 5.2.2 Cyclopropyl Activated Precursors
142 5.2.3 Fragmentation of the Cyclopropane Precursors
146 5.2.4 Cooperatively Activated Cyclopropane Precursors
147 5.3 Formation of Carbonyl Groups
151 5.3.1 Cyclopropylcarbinyl Precursors
151 5.3.2 Cooperatively Activated Precursors
156 5.4 Retrosynthetic Account
162 References
163 6 Cyclobutane Derivatives 167 6.1 Grandisol Syntheses
167 6.2 Cyclobutane Synthetic Intermediates
169 6.3 Retrosynthetic Account
183 References
184 7 Cyclopentanes 187 7.1 Vinylcyclopropane-Cyclopentene Rearrangement
187 7.1.1 Cyclopropylcarbinyl Activated Precursors
187 7.1.2 Cooperatively Activated Precursors
188 7.2 Cycloaddition Reactions
221 7.2.1 Cyclopropylcarbinyl Activated Precursors
221 7.2.2 Cooperatively Activated Precursors
221 7.3 Modification of Substituents
223 7.3.1 N onactivated Cyclopropane Precursors
223 7.3.2 Cyclopropylcarbinyl Activated Precursors
224 7.3.3 Cooperatively Activated Precursors
231 7.3.4 Fragmentation Reactions
245 7.4 Retrosynthetic Account
246 References
246 8 Cyclohexanes 251 8.1 Intramolecular Cyclization Reactions
251 8.2 Cycloaddition Reactions
255 8.3 Modification of Substituents
269 8.3.1 Cyclopropylcarbinyl Activated Precursors
269 8.3.2 Cyclopropyl Activated Precursors
275 8.3.3 Cooperatively Activated Precursors
277 8.4 Retrosynthetic Account
282 References
283 9 Cycloheptanes 285 9.1 Divinylcyclopropane-Cycloheptadiene Rearrangement
285 9.2 Cycloaddition Reactions
315 9.3 Modification of Substituents
318 9.3.1 Nonactivated Cyclopropane Precursors
318 9.3.2 Cyclopropylcarbinyl Activated Precursors
318 9.3.3 Cyclopropyl Activated Precursors
323 9.3.4 Cooperatively Activated Precursors
325 9.4 Retrosynthetic Account
329 References
330 10 Cyclooctanes and Larger Carbocycles 333 10.1 Cycloaddition Reactions
333 10.2 Modification of Substituents
334 10.2.1 Cyclopropylcarbinyl Activated Precursors
334 10.2.2 Cyclopropyl Activated Precursors
338 10.3 Retrosynthetic Account
340 References
340 11 Heterocyclic Compounds 341 11.1 Intramolecular Cyclization Reactions
341 11.1.1 Nonactivated Cyclopropane Precursors
341 11.1.2 Cyclopropylcarbinyl Activated Precursors
342 11.1.3 Cyclopropyl Activated Precursors
378 11.1.4 Cooperatively Activated Precursors
380 11.2 Cycloaddition Reactions
387 11.2.1 Cyclopropylcarbinyl Activated Precursors
387 11.2.2 Cooperatively Activated Precursors
390 11.3 Modification of Substituents
400 11.3.1 Cyclopropylcarbinyl Activated Substrates
400 11.3.2 Cyclopropyl Activated Substrates
402 11.3.3 Cooperatively Activated Substrates
402 11.4 Retrosynthetic Account
409 References
410 CONCLUSION 415 AUTHOR Index 417