Methods and Applications of Cycloaddition Reactions in Organic Syntheses

Advanced tools for developing new functional materials andapplications in chemical research, pharmaceuticals, and materialsscience Cycloadditions are among the most useful tools for organic chemists, enabling them to build carbocyclic and heterocyclic structures. These structures can then be used to develop a broad range of functional materials, including pharmaceuticals, agrochemicals, dyes, and optics. With contributions from an international team of leading experts and pioneers in cycloaddition chemistry, this book brings together and reviews recent advances, trends, and emerging research in the field. Methods and Applications of Cycloaddition Reactions in OrganicSyntheses focuses on two component cycloadditions, with chapters covering such topics as: N 1 unit transfer reaction to CC double bonds [3+2] Cycloaddition of , –unsaturated metal–carbene complexes Formal [3+3] cycloaddition approach to natural product synthesis Development of new methods for the construction of heterocycles based on cycloaddition reaction of 1,3–dipoles Cycloreversion approach for preparation of large –conjugatedcompounds Transition metal–catalyzed or mediated [5+1] cycloadditions Readers will learn methods for seamlessly executing importantreactions such as Diels–Alder and stereoselective dipolar reactionsin order to fabricate heterocyclic compounds, natural products, andfunctional molecules. The book not only features cutting–edge topics,but also important background information, such as thecontributors process for developing new methodologies, to help novices become fully adept in the field. References at the end of each chapter lead to original research papers and reviews for facilitating further investigation of individual topics. Covering the state of the science and technology, Methods andApplications of Cycloaddition Reactions in Organic Syntheses enables synthetic organic chemists to advance their research and develop new functional materials and applications in chemical research, pharmaceuticals, and materials science.

PREFACE ix CONTRIBUTORS xi PART I [2+1] CYCLOADDITION 1 [2+1]–TYPE CYCLOPROPANATION REACTIONS 1 Akio Kamimura 2 N1 UNIT TRANSFER REACTION TO C——C DOUBLE BONDS 67 Satoshi Minakata, Youhei Takeda, and Kensuke Kiyokawa PART II [2+2] CYCLOADDITION 3 LEWIS BASE CATALYZED ASYMMETRIC FORMAL [2þ2] CYCLOADDITIONS 89 Andrew D. Smith, James Douglas, Louis C. Morrill, and Edward Richmond PART III [2+2] AND [4+2]/[2+2] CYCLOADDITION 4 CATALYTIC [2þ2] CYCLOADDITION OF SILYL ENOL ETHERS 115 Yosuke Yamaoka and Kiyosei Takasu PART IV [3+2] CYCLOADDITION 5 [3þ2] CYCLOADDITION OF a,b–UNSATURATED METAL–CARBENE COMPLEXES 135 Ryukichi Takagi and Manabu Abe 6 GEOMETRY–CONTROLLED CYCLOADDITION OF C–ALKOXYCARBONYL NITRONES: SYNTHETIC STUDIES ON NONPROTEINOGENIC AMINO ACIDS 151 Osamu Tamura 7 RECENT ADVANCES IN CATALYTIC ASYMMETRIC 1,3–DIPOLAR CYCLOADDITIONS OF AZOMETHINE IMINES, NITRILE OXIDES, DIAZOALKANES, AND CARBONYL YLIDES 175 Hiroyuki Suga and Kennosuke Itoh 8 CONDENSATION OF PRIMARY NITRO COMPOUNDS TO ISOXAZOLE DERIVATIVES: STOICHIOMETRIC TO CATALYTIC 205 Francesco De Sarlo and Fabrizio Machetti 9 CARBAMOYLNITRILE OXIDE AND INVERSE ELECTRON–DEMAND 1,3–DIPOLAR CYCLOADDITION 223 Nagatoshi Nishiwaki and Haruyasu Asahara PART V [3+2], [3+3], AND [4+2] CYCLOADDITION 10 CYCLOADDITION REACTIONS OF SMALL RINGS 241 Steven D. R. Christie and Hayley T. A. Watson PART VI [3+2] AND [5+1] CYCLOADDITION 11 DEVELOPMENT OF NEW METHODS FOR THE CONSTRUCTION OF HETEROCYCLES BASED ON CYCLOADDITION REACTION OF 1,3–DIPOLES 263 Yutaka Ukaji and Takahiro Soeta PART VII [3+3] CYCLOADDITION 12 A FORMAL [3þ3] CYCLOADDITION APPROACH TO NATURAL PRODUCT SYNTHESIS 283 Jun Deng, Xiao–Na Wang, and Richard P. Hsung PART VIII [4+2] CYCLOADDITION 13 [4þ2] CYCLOADDITION CHEMISTRY OF SUBSTITUTED FURANS 355 Scott Bur and Albert Padwa 14 SYNTHESIS OF SUBSTITUTED OLIGOACENES VIA DIELS–ALDER REACTIONS AND SUBSTITUENT EFFECTS ON MOLECULAR STRUCTURE, PACKING ARRANGEMENT, AND SOLID–STATE OPTICAL PROPERTIES 407 Chitoshi Kitamura 15 CYCLOREVERSION APPROACH FOR PREPARATION OF LARGE p–CONJUGATED COMPOUNDS 429 Hidemitsu Uno PART IX [4+2]/[3+2] CYCLOADDITION 16 TANDEM [4þ2]/[3þ2] CYCLOADDITIONS 471 Ramil Y. Baiazitov and Scott E. Denmark PART X [5+1] CYCLOADDITION 17 TRANSITION METAL–CATALYZED OR –MEDIATED [5þ1] CYCLOADDITIONS 551 Xu–Fei Fu and Zhi–Xiang Yu PART XI [4+3] CYCLOADDITION 18 [4þ3] CYCLOADDITIONS OF ENOLSILANE DERIVATIVES 565 Sarah Y. Y. Lam and Pauline Chiu 19 APPLICATION OF THE [4þ3] CYCLOADDITION REACTION TO THE SYNTHESIS OF NATURAL PRODUCTS 599 Darin E. Jones and Michael Harmata PART XII [5+2] CYCLOADDITION 20 RECENT DEVELOPMENTS IN THE [5þ2] CYCLOADDITION 631 Hervé Clavier and Hélène Pellissier INDEX 655

NAGATOSHI NISHIWAKI, PhD, is Professor of Chemistry at Kochi University of Technology, Japan. Dr. Nishiwaki has published over ninety scientific papers, twenty reviews and book chapters, and ten papers in chemical education. In addition, he has presented his research results at many scientific conferences.