Organic reaction mechanisms : 40 solved cases / M. Gómez Gallego, M. Angel Sierra.

Format:

Book

Author/Creator:

Gómez Gallego, Mar.

Contributor:

Sierra, Miguel A. (Miguel Angel)

Language:

English

Subjects (All):

Organic reaction mechanisms.

Physical Description:

x, 290 pages : illustrations ; 25 cm

Place of Publication:

Berlin ; New York : Springer, [2004]

Summary:

Organic Reaction Mechanisms shows readers how to interpret the experimental data obtained from an organic reaction, and specifically how an organic reaction mechanism can be considered or rejected based on the analysis of the experimental evidence. Examining a series of selected examples of mechanisms, Organic Reaction Mechanisms focuses on real cases and discusses them in detail, following the same methodology: introduction, experimental data and discussion. The examples are arranged to elucidate key aspects of organic reaction mechanisms. The authors employ all the types of information that the authors of the original work considered useful and necessary, including kinetic and thermodynamic data, isotopic labelling and organic reactivity. The book makes an excellent primer for advanced undergraduates in chemistry who are preparing for exams and is also be useful for graduate students and instructors.

Contents:

Case 1. A Surprise in the Synthesis of Guanacastepene A 1

Case 2. Sulfenylation of Indole 7

Case 3. Substrate Selective Reactions in the Presence of Lewis Acids 13

Case 4. Diastereoselective Reductions of [beta]-Ketoesters 21

Case 5. Rearrangements from Tetrahydropyran Derivatives 27

Case 6. Stereospecific Substitution Reactions of Epoxy Sulfides 33

Case 7. NaBH[subscript 4] Reduction of [alpha, beta]-Unsaturated Chromium Carbene Complexes 39

Case 8. Addition of Hydroxylamines to [alpha, beta]-Unsaturated Esters 47

Case 9. Solvolysis of Electron-Deficient Norbornyl Triflates 55

Case 10 Nucleophile Versus Base Catalysis 63

Case 11. The Hydrolysis of p-Substituted Styrene Oxides 69

Case 12. Elimination Reactions of Benzaldehyde O-Benzoyloximes 79

Case 13. Oxygen Versus Sulfur Stabilization of Carbenium Ions 87

Case 14. Cyclization of 2,3-Dibenzylidenesuccinates 97

Case 15. Oxazoline N-Oxides as Dipoles in [3+2] Cycloadditions 101

Case 16. Light-Induced Cycloadditions of N-Phthaloyl [alpha]-Amino Acids 107

Case 17. Change in Rate-Determining Step in an E1cB Mechanism: Aminolysis of Sulfamate Esters 113

Case 18. Unusual Diels-Alder Reactivity of Acyclic 2-Azadienes 119

Case 19. Chelate-Controlled Carbonyl Addition Reactions 125

Case 20. Esterification of Carboxylic Acids with Dimethyl Carbonate and DBU 131

Case 21. A Hammett Analysis in a Multistep Reaction: Rhodium(II)-Catalyzed Decomposition of [alpha]-Diazo Esters 139

Case 22. Tandem Cycloadditions with Nitronates 145

Case 23. Hydrolysis of 2-Aminobenzoate Esters 153

Case 24. Rearrangements of Cyclobutenones 159

Case 25. Epoxi Ester-Orthoester Rearrangement 163

Case 26. 2-Chloro-1,3,5-triazines as Activating Groups of Carboxylic Acids in the Formation of Peptide Bonds 169

Case 27. Acid-Catalyzed Isomerization of Imines 177

Case 28. A Dearomatizing Disrotatory Electrocyclic Ring Closure 183

Case 29. Stereoselective Debromination of Vicinal Dibromides 189

Case 30. Diels-Alder Reactions of N-Acyl-1,2,4,5-tetrazines 197

Case 31. Stereoselective Synthesis of 2-Acylaziridines 203

Case 32. The Baylis-Hillman Reaction 211

Case 33. The Rate-Determining Step in the S[subscript N]Ar Reaction 217

Case 34. Helicenophanes and their Racemization 225

Case 35. Solvolysis of Vinyl Iodonium Salts 231

Case 36. Vicarious Nucleophilic Substitution 237

Case 37. Base-promoted HF Elimination from 4-Fluoro-4-(4'-nitrophenyl)butan-2-one 243

Case 38. Substitution of [beta]-Halostyrenes by MeS[superscript -] 251

Case 39. Periodinane-Mediated Cyclization of Anilides 259

Case 40. Solvolysis of 8-Deltacyclyl Brosylates 269.

Notes:

Includes bibliographical references and index.

ISBN:

3540003525

OCLC:

53276603