Page 24 - Advanced Organic Chemistry Part B - Reactions & Synthesis

xxvi General References............................................................................................... 358
Problems ............................................................................................................... 358
Contents

Chapter 5. Reduction of Carbon-Carbon Multiple Bonds, Carbonyl
Groups, and Other Functional Groups ...................... 367

Introduction........................................................................................................... 367
5.1. Addition of Hydrogen at Carbon-Carbon Multiple Bonds.......................... 368
5.1.1. Hydrogenation Using Heterogeneous Catalysts ............................... 368
5.1.2. Hydrogenation Using Homogeneous Catalysts ................................ 374
5.1.3. Enantioselective Hydrogenation........................................................ 376
5.1.4. Partial Reduction of Alkynes............................................................ 387
5.1.5. Hydrogen Transfer from Diimide ..................................................... 388
5.2. Catalytic Hydrogenation of Carbonyl and Other Functional Groups ......... 390
5.3. Group III Hydride-Donor Reagents ............................................................. 396
5.3.1. Comparative Reactivity of Common Hydride
Donor Reagents ................................................................................. 396
5.3.2. Stereoselectivity of Hydride Reduction............................................ 407
5.3.3. Enantioselective Reduction of Carbonyl Compounds...................... 415
5.3.4. Reduction of Other Functional Groups by Hydride Donors............ 422
5.4. Group IV Hydride Donors ........................................................................... 425
5.4.1. Reactions Involving Silicon Hydrides .............................................. 425
5.4.2. Hydride Transfer from Carbon ......................................................... 429
5.5. Reduction Reactions Involving Hydrogen Atom Donors............................ 431
5.6. Dissolving-Metal Reductions ....................................................................... 434
5.6.1. Addition of Hydrogen ....................................................................... 435
5.6.2. Reductive Removal of Functional Groups ....................................... 439
5.6.3. Reductive Coupling of Carbonyl Compounds.................................. 444
5.7. Reductive Deoxygenation of Carbonyl Groups........................................... 452
5.7.1. Reductive Deoxygenation of Carbonyl Groups to Methylene......... 452
5.7.2. Reduction of Carbonyl Compounds to Alkenes............................... 454
5.8. Reductive Elimination and Fragmentation................................................... 457
Problems ............................................................................................................... 462

Chapter 6. Concerted Cycloadditions, Unimolecular Rearrangements,
and Thermal Eliminations .................................. 473

Introduction........................................................................................................... 473
6.1. Diels-Alder Reactions................................................................................... 474
6.1.1. The Diels-Alder Reaction: General Features.................................... 474
6.1.2. Substituent Effects on the Diels-Alder Reaction.............................. 475
6.1.3. Lewis Acid Catalysis of the Diels-Alder Reaction .......................... 481
6.1.4. The Scope and Synthetic Applications
of the Diels-Alder Reaction .............................................................. 487
6.1.5. Diastereoselective Diels-Alder Reactions
Using Chiral Auxiliaries ................................................................... 499
6.1.6. Enantioselective Catalysts for Diels-Alder Reactions...................... 505
6.1.7. Intramolecular Diels-Alder Reactions............................................... 518