{"product_id":"molecular-rearrangements-in-organic-synthesis-isbn-9781118347966","title":"Molecular Rearrangements in Organic Synthesis","description":"\u003cp\u003eDesigned for practitioners of organic synthesis, this book helps chemists understand and take advantage of rearrangement reactions to enhance the synthesis of useful chemical compounds.\u003cbr\u003e\u003cbr\u003e\u003c\/p\u003e \u003cul\u003e \u003cli\u003eProvides ready access to the genesis, mechanisms, and synthetic utility of rearrangement reactions\u003c\/li\u003e \u003cli\u003eEmphasizes strategic synthetic planning and implementation\u003c\/li\u003e \u003cli\u003eCovers 20 different rearrangement reactions\u003c\/li\u003e \u003cli\u003eIncludes applications for synthesizing compounds useful as natural products, medicinal compounds, functional materials, and physical organic chemistry\u003c\/li\u003e \u003c\/ul\u003e \u003cp\u003eLIST OF CONTRIBUTORS xvii\u003c\/p\u003e \u003cp\u003ePREFACE xxi\u003c\/p\u003e \u003cp\u003e\u003cb\u003ePART 1 1,2-MIGRATIONS 1\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e\u003cb\u003e1 Pinacol and Semipinacol Rearrangements in Total Synthesis 3\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e1.1 Introduction 3\u003c\/p\u003e \u003cp\u003e1.2 Pinacol Reaction 4\u003c\/p\u003e \u003cp\u003e1.3 Semipinacol Rearrangement 15\u003c\/p\u003e \u003cp\u003e1.4 Conclusion 30\u003c\/p\u003e \u003cp\u003eReferences 32\u003c\/p\u003e \u003cp\u003e\u003cb\u003e2 Baeyer–Villiger (BV) Oxidation\/Rearrangement in Organic Synthesis 35\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e2.1 Introduction 35\u003c\/p\u003e \u003cp\u003e2.2 Mechanism 35\u003c\/p\u003e \u003cp\u003e2.3 Synthetic Applications 37\u003c\/p\u003e \u003cp\u003e2.4 Summary and Outlook 55\u003c\/p\u003e \u003cp\u003eReferences 55\u003c\/p\u003e \u003cp\u003e\u003cb\u003e3 The Wolff Rearrangement: Tactics, Strategies and Recent Applications in Organic Synthesis 59\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e3.1 Introduction 59\u003c\/p\u003e \u003cp\u003e3.2 Tactics and Strategies via the Wolff Rearrangement 60\u003c\/p\u003e \u003cp\u003e3.3 Mechanistic Features and Selectivity Issues of the Wolff Rearrangement 63\u003c\/p\u003e \u003cp\u003e3.4 Preparation of α-Diazocarbonyl Compounds 64\u003c\/p\u003e \u003cp\u003e3.5 Recent Synthetic Applications of the Wolff Rearrangement 67\u003c\/p\u003e \u003cp\u003e3.6 Conclusion and Outlook 80\u003c\/p\u003e \u003cp\u003eReferences 81\u003c\/p\u003e \u003cp\u003e\u003cb\u003e4 Alkyl and Acyl Azide Rearrangements 85\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e4.1 Introduction 85\u003c\/p\u003e \u003cp\u003e4.2 Alkyl Azide Rearrangements 86\u003c\/p\u003e \u003cp\u003e4.3 Acyl Azide Rearrangements 98\u003c\/p\u003e \u003cp\u003e4.4 Hofmann Rearrangement 102\u003c\/p\u003e \u003cp\u003e4.5 Lossen Rearrangement 104\u003c\/p\u003e \u003cp\u003e4.6 Conclusion 107\u003c\/p\u003e \u003cp\u003eReferences 108\u003c\/p\u003e \u003cp\u003e\u003cb\u003e5 Beckmann Rearrangements and Fragmentations in Organic Synthesis 111\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e5.1 Introduction 111\u003c\/p\u003e \u003cp\u003e5.2 Strategic Planning: A Historical Perspective 118\u003c\/p\u003e \u003cp\u003e5.3 Recent Applications Toward the Synthesis of Natural Products 121\u003c\/p\u003e \u003cp\u003e5.4 Access to Diverse Scaffolds via the Beckmann Reaction 129\u003c\/p\u003e \u003cp\u003e5.4.1 Diterpene Hydrocarbons 129\u003c\/p\u003e \u003cp\u003e5.5 Formation of Heterocyclic Scaffolds 136\u003c\/p\u003e \u003cp\u003e5.6 Synthesis of Functional Groups 140\u003c\/p\u003e \u003cp\u003e5.7 Summary and Outlook 144\u003c\/p\u003e \u003cp\u003eReferences 145\u003c\/p\u003e \u003cp\u003e\u003cb\u003e6 Brook Rearrangement 151\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e6.1 Introduction 151\u003c\/p\u003e \u003cp\u003e6.2 Mechanism 152\u003c\/p\u003e \u003cp\u003e6.3 Methods for Generation of α-Silyl Alkoxides 153\u003c\/p\u003e \u003cp\u003e6.4 Synthetic Reactions Using Brook Rearrangements in the Reactions of Acylsilanes with Nucleophiles 154\u003c\/p\u003e \u003cp\u003e6.5 Synthetic Reactions Using Brook Rearrangements Triggered by Deprotonation of α-Silyl Alcohols 166\u003c\/p\u003e \u003cp\u003e6.6 Synthetic Reactions Using Brook Rearrangements Triggered by Addition of Silylmetallic Reagents 169\u003c\/p\u003e \u003cp\u003e6.7 Synthetic Reactions Using Brook Rearrangements in β-Silyl Alkoxides Generated via Regioselective \u003ci\u003eβ\u003c\/i\u003e-Ring-Opening of α, \u003ci\u003eβ\u003c\/i\u003e-Epoxysilanes by a Nucleophile 172\u003c\/p\u003e \u003cp\u003e6.8 Synthetic Reactions Using Brook Rearrangements in α-Silyl Alkoxides Generated by a Base-Induced Ring-Opening of alpha;, \u003ci\u003eβ\u003c\/i\u003e-Epoxysilanes 173\u003c\/p\u003e \u003cp\u003e6.9 Conclusion 176\u003c\/p\u003e \u003cp\u003eReferences 178\u003c\/p\u003e \u003cp\u003e\u003cb\u003ePART II 1,2-MIGRATIONS VIA THREE-MEMBERED RINGS 183\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e\u003cb\u003e7 The Quasi-Favorskii Rearrangement 185\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e7.1 Introduction 185\u003c\/p\u003e \u003cp\u003e7.2 Retrons of the Quasi-Favorskii Rearrangement 191\u003c\/p\u003e \u003cp\u003e7.3 Mechanistic Considerations in the Quasi-Favorskii Rearrangement 192\u003c\/p\u003e \u003cp\u003e7.4 The Preparation of Substrates for the Quasi-Favorskii Rearrangement 193\u003c\/p\u003e \u003cp\u003e7.5 Applications of the Quasi-Favorskii Rearrangement in Synthesis 199\u003c\/p\u003e \u003cp\u003e7.6 Conclusions and Prospects 220\u003c\/p\u003e \u003cp\u003eAcknowledgments 222\u003c\/p\u003e \u003cp\u003eReferences 222\u003c\/p\u003e \u003cp\u003e\u003cb\u003e8 The Ramberg–Bäcklund Reaction 227\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e8.1 Introduction 227\u003c\/p\u003e \u003cp\u003e8.2 Methods to Synthesize Sulfones as RBR Precursors 229\u003c\/p\u003e \u003cp\u003e8.3 Variations of the RBR 231\u003c\/p\u003e \u003cp\u003e8.4 Mechanistic Evaluation of the RBR 233\u003c\/p\u003e \u003cp\u003e8.5 Strategic Considerations Relevant to the Use of the RBR in Synthesis 234\u003c\/p\u003e \u003cp\u003e8.6 Utility, Scope, and Limitations of the RBR 236\u003c\/p\u003e \u003cp\u003e8.7 Recent Applications of the RBR in the Synthesis of Complex Target Structures 246\u003c\/p\u003e \u003cp\u003e8.7.1 Fawcettidine 246\u003c\/p\u003e \u003cp\u003e8.8 Concluding Remarks 254\u003c\/p\u003e \u003cp\u003eAcknowledgments 256\u003c\/p\u003e \u003cp\u003eReferences 256\u003c\/p\u003e \u003cp\u003e\u003cb\u003e9 Applications of Di-\u003c\/b\u003e\u003cb\u003eл-Methane and Related Rearrangement Reactions in Chemical Synthesis 261\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e9.1 Introduction: The Basic Process and its Variants 261\u003c\/p\u003e \u003cp\u003e9.2 Mechanistic Features and Competing Reactions 265\u003c\/p\u003e \u003cp\u003e9.3 Structural Requirements of Substrates and Matters of Regio- and Stereochemistry 271\u003c\/p\u003e \u003cp\u003e9.4 Synthetic Routes to Substrates and Applications in Synthesis 277\u003c\/p\u003e \u003cp\u003e9.5 Outlook 284\u003c\/p\u003e \u003cp\u003eReferences 285\u003c\/p\u003e \u003cp\u003e\u003cb\u003ePARTIII 1,3-TRANSPOSITIONS 289\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e\u003cb\u003e10 Payne Rearrangement 291\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e10.1 Background on the Payne Rearrangement 291\u003c\/p\u003e \u003cp\u003e10.2 Synthetic Applications of 2,3-Epoxy Alcohols 295\u003c\/p\u003e \u003cp\u003e10.3 Utilization of the Payne Rearrangement for the Preparation of Fluorine-Containing Compounds 307\u003c\/p\u003e \u003cp\u003e10.4 Conclusion 317\u003c\/p\u003e \u003cp\u003eReferences 318\u003c\/p\u003e \u003cp\u003e\u003cb\u003e11 Vinylcyclopropane–Cyclopentene Rearrangement 323\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e11.1 Introduction 323\u003c\/p\u003e \u003cp\u003e11.2 Thermal VCP–CP Rearrangement 324\u003c\/p\u003e \u003cp\u003e11.3 Acid-Mediated VCP–CP Rearrangement 328\u003c\/p\u003e \u003cp\u003e11.4 Mechanisms 330\u003c\/p\u003e \u003cp\u003e11.5 Heteroatom-Containing Analogues of the VCP–CP Rearrangement 334\u003c\/p\u003e \u003cp\u003e11.6 Applications in Synthesis 336\u003c\/p\u003e \u003cp\u003e11.7 Photochemical VCP–CP Rearrangement 340\u003c\/p\u003e \u003cp\u003e11.8 Metal-Catalyzed VCP–CP Rearrangement 346\u003c\/p\u003e \u003cp\u003e11.9 Heteroatom Variants of the Metal-Catalyzed VCP–CP Rearrangement 354\u003c\/p\u003e \u003cp\u003e11.10 Summary and Outlook 359\u003c\/p\u003e \u003cp\u003eReferences 360\u003c\/p\u003e \u003cp\u003e\u003cb\u003e12 Ferrier Carbocyclization Reaction 363\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e12.1 Introduction 363\u003c\/p\u003e \u003cp\u003e12.2 General Discussion and Mechanistic Features 365\u003c\/p\u003e \u003cp\u003e12.3 Synthetic Strategies Based on the Ferrier Carbocyclization Reaction 373\u003c\/p\u003e \u003cp\u003e12.4 Methodologies for Assembling the Ferrier Carbocyclization Reaction Substrates 377\u003c\/p\u003e \u003cp\u003e12.5 Applications of the Ferrier Carbocyclization Reaction in Natural Product Synthesis 380\u003c\/p\u003e \u003cp\u003e12.6 Conclusion 397\u003c\/p\u003e \u003cp\u003eReferences 398\u003c\/p\u003e \u003cp\u003e\u003cb\u003ePARTIV [3,3]- AND [2,3]-SIGMATROPIC REARRANGEMENTS 401\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e\u003cb\u003e13 The Claisen Rearrangement 403\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e13.1 Introduction 403\u003c\/p\u003e \u003cp\u003e13.2 Strategic Planning for the Claisen Rearrangement Reaction 407\u003c\/p\u003e \u003cp\u003e13.3 Mechanistic Features of the Claisen Rearrangement Reaction 409\u003c\/p\u003e \u003cp\u003e13.4 Methodologies for Synthesis of Claisen Rearrangement Substrates 417\u003c\/p\u003e \u003cp\u003e13.5 Applications of the Claisen Rearrangement Reaction in Target-Oriented Synthesis 421\u003c\/p\u003e \u003cp\u003e13.6 Conclusions 426\u003c\/p\u003e \u003cp\u003eReferences 427\u003c\/p\u003e \u003cp\u003e\u003cb\u003e14 [3,3]-Sigmatropic Rearrangements with Heteroatom–Heteroatom Bonds 431\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e14.1 Introduction 431\u003c\/p\u003e \u003cp\u003e14.2 [3,3]-Sigmatropic Rearrangements of N–O Bonds 434\u003c\/p\u003e \u003cp\u003e14.3 [3,3]-Sigmatropic Rearrangements of N–N Bonds 445\u003c\/p\u003e \u003cp\u003e14.4 [3,3]-Rearrangements of N–N Bond Fragments that Eliminate N2 451\u003c\/p\u003e \u003cp\u003e14.5 Summary 454\u003c\/p\u003e \u003cp\u003eReferences 455\u003c\/p\u003e \u003cp\u003e\u003cb\u003e15 [2,3]-Rearrangements of Ammonium Zwitterions 459\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e15.1 Introduction 459\u003c\/p\u003e \u003cp\u003e15.2 [2,3]-Meisenheimer Rearrangement of Amine N-Oxides 460\u003c\/p\u003e \u003cp\u003e15.3 [2,3]-Stevens Rearrangement of Ammonium Ylides 479\u003c\/p\u003e \u003cp\u003e15.4 Conclusion and Outlook 492\u003c\/p\u003e \u003cp\u003eReferences 493\u003c\/p\u003e \u003cp\u003e\u003cb\u003e16 Oxonium Ylide Rearrangements in Synthesis 497\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e16.1 Introduction 497\u003c\/p\u003e \u003cp\u003e16.2 Applications in Synthesis: Oxonium Ylide [2,3]-Sigmatropic Rearrangements 507\u003c\/p\u003e \u003cp\u003e16.3 Applications in Synthesis: Oxonium Ylide [1,2]-Stevens Rearrangements 528\u003c\/p\u003e \u003cp\u003e16.4 Concluding Remarks 535\u003c\/p\u003e \u003cp\u003eReferences 536\u003c\/p\u003e \u003cp\u003e\u003cb\u003e17 The [2,3]-Wittig Rearrangement 539\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e17.1 Introduction 539\u003c\/p\u003e \u003cp\u003e17.2 [2,3]-Wittig Rearrangement of Allyl Propargyl Ethers 541\u003c\/p\u003e \u003cp\u003e17.3 Factors Determining [2,3]-Wittig Versus [1,2]-Wittig Rearrangement 544\u003c\/p\u003e \u003cp\u003e17.4 Acyclic [2,3]-Wittig Rearrangement of Propargyl-Allyl Ethers 547\u003c\/p\u003e \u003cp\u003e17.5 [2,3]-Wittig–Still Rearrangement 552\u003c\/p\u003e \u003cp\u003e17.6 Asymmetric [2,3]-Wittig Rearrangement 554\u003c\/p\u003e \u003cp\u003e17.7 Aza-[2,3]-Wittig Rearrangement 555\u003c\/p\u003e \u003cp\u003e17.8 Other Wittig Rearrangements and Miscellaneous 560\u003c\/p\u003e \u003cp\u003e17.9 Conclusion 565\u003c\/p\u003e \u003cp\u003eReferences 565\u003c\/p\u003e \u003cp\u003e\u003cb\u003e18 The Mislow–Evans Rearrangement 569\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e18.1 Introduction 569\u003c\/p\u003e \u003cp\u003e\u003cb\u003ePart 1 Mechanistic Aspects and the [2,3] Nature of the Rearrangement 571\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e18.2 Configurational Lability of Allylic Sulfoxides 571\u003c\/p\u003e \u003cp\u003e18.3 Deuterium Labeling to Track [2,3] Pathway 573\u003c\/p\u003e \u003cp\u003e18.4 Transition State Features 573\u003c\/p\u003e \u003cp\u003e18.5 Equilibrium Between Sulfoxide and Sulfenate 576\u003c\/p\u003e \u003cp\u003e18.6 Chirality Transfer 579\u003c\/p\u003e \u003cp\u003e\u003cb\u003ePart 2 Synthetic Considerations and Applications 580\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e18.7 Alkene Stereoselectivity 580\u003c\/p\u003e \u003cp\u003e18.8 Diastereoface Selectivity in the Rearrangement 583\u003c\/p\u003e \u003cp\u003e18.9 Epimerizations via Mislow–Evans Rearrangement Sequences 591\u003c\/p\u003e \u003cp\u003e18.10 Vinyl Anion Synthons Accessible via Mislow–Evans Rearrangement 593\u003c\/p\u003e \u003cp\u003e18.11 Sequential Processes Incorporating the Mislow–Evans Rearrangement 598\u003c\/p\u003e \u003cp\u003e18.12 Heteroatom [2,3]-Rearrangement Variants 614\u003c\/p\u003e \u003cp\u003e18.13 [2,3]-Rearrangements of Propargyl and Allenyl Sulfenates and Sulfoxides 620\u003c\/p\u003e \u003cp\u003e18.14 Conclusion 622\u003c\/p\u003e \u003cp\u003eReferences 622\u003c\/p\u003e \u003cp\u003e\u003cb\u003ePART V IPSO REARRANGEMENTS 627\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e\u003cb\u003e19 Smiles Rearrangements 629\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e19.1 Introduction 629\u003c\/p\u003e \u003cp\u003e19.2 Scope and Mechanistic Features 632\u003c\/p\u003e \u003cp\u003e19.3 Application of Smiles Rearrangements 635\u003c\/p\u003e \u003cp\u003e19.4 Conclusion 657\u003c\/p\u003e \u003cp\u003eReferences 658\u003c\/p\u003e \u003cp\u003e\u003cb\u003e20 Pummerer-Type Reactions as Powerful Tools in Organic Synthesis 661\u003c\/b\u003e\u003c\/p\u003e \u003cp\u003e20.1 Introduction 661\u003c\/p\u003e \u003cp\u003e20.2 Classical Pummerer Reaction 662\u003c\/p\u003e \u003cp\u003e20.3 Vinylogous Pummerer Reaction 674\u003c\/p\u003e \u003cp\u003e20.4 Interrupted and Additive Pummerer Reactions 680\u003c\/p\u003e \u003cp\u003e20.5 Connective Pummerer Reaction 687\u003c\/p\u003e \u003cp\u003e20.6 Pummerer Rearrangement in Multiple-Reaction Processes 693\u003c\/p\u003e \u003cp\u003e20.7 Other Pummerer Rearrangements 696\u003c\/p\u003e \u003cp\u003e20.8 Summary and Outlook 700\u003c\/p\u003e \u003cp\u003eReferences 700\u003c\/p\u003e \u003cp\u003eINDEX 703\u003c\/p\u003e \"a valuable teaching resource to those engaged in mentoring of advanced undergraduates and postgraduates........an accessible entry to the subject area for all students and practitioners of the art. Highly recommended.\" (Angewandte Chemie 2016) \u003cb\u003eChristian M. Rojas, PhD,\u003c\/b\u003e is Professor of Chemistry at Barnard College. He obtained his Ph.D. at Indiana University in 1995 and did postdoctoral studies at the Massachusetts Institute of Technology and then at The Scripps Research Institute. Professor Rojas began his independent career at Barnard College in 1997. His research explores the use of acyl nitrenes for the synthesis of amino sugars. \u003cp\u003eAmong the most venerable reactions of modern organic chemistry, molecular rearrangements offer ways for the rapid assembly of synthetically challenging substructures within organic molecules and continue to be an active area of research. Current investigations have probed the development of catalysts for the promotion of rearrangement reactions and the use of rearrangements in the preparation organic compounds such as biologically active natural products.\u003cbr\u003e\u003cbr\u003eDesigned for practitioners of organic synthesis, \u003ci\u003eMolecular Rearrangements in Organic Synthesis\u003c\/i\u003e helps chemists understand and take advantage of rearrangement reactions to enhance the synthesis of useful chemical compounds. The book emphasizes ways that a given molecular rearrangement can be incorporated into synthetic planning and how that synthetic plan can be put into practice. Organic synthesis is construed broadly, including synthesis of natural products and medicinally important compounds and also preparation of organic compounds with unusual structures or high levels of strain and for use in physical organic chemical studies. Covering 20 different rearrangement reactions, the book includes instructive examples from the recent literature as well as methods for preparing the rearrangement precursors. In this way, the book is a useful handbook for applying rearrangements to the practice of synthetic organic chemistry.\u003cbr\u003e\u003cbr\u003eFeaturing contributions from leaders in the research and application of rearrangement reactions, the book represents a valuable reference and resource for anyone involved in the practice of organic chemistry and offers a number of benefits that include:\u003cbr\u003e\u003cbr\u003e\u003c\/p\u003e \u003cul\u003e \u003cli\u003eReady access to the genesis, mechanisms, and synthetic utility of rearrangement reactions\u003c\/li\u003e \u003cli\u003eGuidance for organic chemists to understand and take advantage of rearrangements to enhance the synthesis of useful chemical compounds\u003c\/li\u003e \u003cli\u003eA clear and interesting point of departure for thought and further investigation\u003c\/li\u003e \u003c\/ul\u003e","brand":"Wiley","offers":[{"title":"Default Title","offer_id":47989649408229,"sku":"NP9781118347966","price":218.95,"currency_code":"USD","in_stock":false}],"thumbnail_url":"\/\/cdn.shopify.com\/s\/files\/1\/1842\/7735\/files\/9781118347966.jpg?v=1761784956","url":"https:\/\/k12savings.com\/es\/products\/molecular-rearrangements-in-organic-synthesis-isbn-9781118347966","provider":"K12savings","version":"1.0","type":"link"}