Details

Asymmetric Synthesis II


Asymmetric Synthesis II

More Methods and Applications
1. Aufl.

von: Mathias Christmann, Stefan Bräse

97,99 €

Verlag: Wiley-VCH
Format: EPUB
Veröffentl.: 17.04.2013
ISBN/EAN: 9783527672592
Sprache: englisch
Anzahl Seiten: 430

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Beschreibungen

After the overwhelming success of 'Asymmetric Synthesis - The Essentials', narrating the colorful history of asymmetric synthesis, this is the second edition with latest subjects and authors. While the aim of the first edition was mainly to honor the achievements of the pioneers in asymmetric syntheses, the aim of this new edition was bringing the current developments, especially from younger colleagues, to the attention of students. The format of the book remained unchanged, i.e. short conceptual overviews by young leaders in their field including a short biography of the authors. The growing multidisciplinary research within chemistry is reflected in the selection of topics including metal catalysis, organocatalysis, physical organic chemistry, analytical chemistry, and its applications in total synthesis. The prospective reader of this book is a graduate or undergraduate student of advanced organic chemistry as well as the industrial chemist who wants to get a brief update on the current developments in the field.
List of Contributors XVII 1 Catalytic Enantioselective Alkylation of Prochiral Ketone Enolates 1 Corey M. Reeves and Brian M. Stoltz Background 1 Strategy and Results 1 Asymmetric Allylic Alkylation in Total Synthesis 4 Conclusions 8 CV of Corey M. Reeves 8 CV of Brian M. Stoltz 8 References 8 2 Point-to-Planar Chirality Transfer in Total Synthesis: Scalable and Programmable Synthesis of Haouamine A and Its Atropisomer 11 Noah Z. Burns and Phil S. Baran Introduction 11 Synthetic Strategy Featuring Point-to-Planar Chirality Transfer 11 Programmable Synthesis of Haouamine A and Its Atropisomer 12 CV of Noah Z. Burns 15 CV of Phil S. Baran 15 References 16 3 Tethered Aminohydroxylation 17 Timothy J. Donohoe and Stefanie Mesch Introduction and Background 17 Tethered Aminohydroxylation 17 a) First Generation of Reoxidants 18 b) N-Sulfonyloxy Carbamates 19 c) Carbonyloxycarbamates as Reoxidants for Osmium 21 Amide-Based Reoxidants 22 Evidence for the Mechanism of the TA Reaction 23 Applications in Organic Synthesis 24 Conclusion and Future Work 24 CV of Timothy J. Donohoe 24 CV of Stefanie Mesch 26 References 26 4 Organocatalyzed Transformations of ?, ?-Unsaturated Carbonyl Compounds through Iminium Ion Intermediates 29 Julian H. Rowley and Nicholas C. O. Tomkinson CV of Nicholas C. O. Tomkinson 33 CV of Julian H. Rowley 33 References 34 5 The Renaissance of Silicon-Stereogenic Silanes: A Personal Account 35 Andreas Weickgenannt and Martin Oestreich Background 35 Results 36 a) Intermolecular Chirality Transfer from Silicon to Carbon: Diastereoselective Palladium(II)-Catalyzed C–Si Bond Formation 36 b) Silicon-Stereogenic Silane as Stereochemical Probe: B(C6F5)3-Catalyzed Carbonyl Reduction 37 c) Kinetic Resolution with Silicon-Stereogenic Silanes: Cu–H-Catalyzed Diastereoselective Si–O Coupling 39 Conclusion 41 CV of Martin Oestreich 41 CV of Andreas Weickgenannt 41 References 41 6 Asymmetric Dienamine Activation 43 Mathias Christmann Introduction 43 Historic Background 43 Results 44 Conclusion 47 CV of Mathias Christmann 47 References 47 7 Asymmetric Brønsted Acid Catalysis 49 Iuliana Atodiresei, Uxue Uria, and Magnus Rueping Introduction and Background 49 Strategy 49 Results 50 Summary 52 CV of Iuliana Atodiresei 52 CV of Uxue Uria 52 CV of Magnus Rueping 53 References 53 8 Quaternary Stereogenic Centers by Enantioselective ?-Carbon Eliminations from tert-Cyclobutanols 55 Nicolai Cramer and Tobias Seiser Background 55 Objective: Enantioselective Formation of Quaternary Stereogenic Centers in Combination with Reactive Alkyl-Rhodium Intermediates 56 Selective Generation of the Alkyl-Rhodium Species and Its Downstream Reactivities 56 CV of Nicolai Cramer 57 CV of Tobias Seiser 59 References 59 9 Total Synthesis of Oseltamivir and ABT-341 Using One-Pot Technology 61 Hayato Ishikawa and Yujiro Hayashi Introduction 61 Results 61 a) Total Synthesis of (?)-Oseltamivir via Two One-Pot Processes 61 b) Total Synthesis of ABT-341 by One-Pot Sequence 63 Conclusions 64 CV of Yujiro Hayashi 65 CV of Hayato Ishikawa 65 References 65 10 Enantioselective Annulations with Chiral N-Mesityl N-Heterocyclic Carbenes 67 Jessada Mahatthananchai and Jeffrey W. Bode Introduction 67 Catalytic Generation of Chiral Enolate Equivalents 68 Catalytic Generation of Homoenolate Equivalents 70 Enantioselective Cascade Reactions Catalyzed by Chiral N-Heterocyclic Carbenes 70 Catalytic Annulations via ?, ?-Unsaturated Acyl Azoliums 72 Conclusions 74 CV of Jeffrey Bode 76 CV of Jessada Mahatthananchai 76 References 76 11 Asymmetric Counteranion-Directed Catalysis (ACDC) 79 Manuel Mahlau and Benjamin List Concept 79 Application of ACDC to Organocatalysis 80 Application of ACDC to Transition Metal Catalysis 81 Application of ACDC to Lewis Acid Catalysis 82 CV of Manuel Mahlau 83 CV of Prof. Dr. Benjamin List 84 References 84 12 Enantioselective Organo-SOMO Catalysis: a Novel Activation Mode for Asymmetric Synthesis 87 David W. C. MacMillan and Sebastian Rendler Background 87 Objective 88 Results 90 CV of David W.C. MacMillan 92 CV of Sebastian Rendler 93 References 93 13 Enantioselective Passerini Reaction 95 Qian Wang, Jieping Zhu, and Mei-Xiang Wang Introduction 95 Background 95 Results 96 Conclusion and Perspective 99 CV of Qian Wang 99 CV of Jieping Zhu 99 CV of Mei-Xiang Wang 100 References 100 14 Rapid Enantiomeric Excess Determination 103 Oliver Trapp CV of Oliver Trapp 106 References 106 15 Asymmetric Catalysis of Reversible Reactions 109 Lukas Hintermann Thermochemistry of Asymmetric Catalyses Close to the Equilibrium 109 Kinetic Modeling of a Reversible Asymmetric Catalytic Reaction 111 Case Study: a Reversible Asymmetric Organocatalytic Reaction 112 Conclusions 115 CV of Lukas Hintermann 115 References 115 16 Exploiting Fluorine Conformational Effects in Organocatalyst Design: The Fluorine–Iminium Ion Gauche Effect 117 Christof Sparr, Lucie E. Zimmer, and Ryan Gilmour CV of C. Sparr 121 CV of L. Zimmer 123 CV of R. Gilmour 123 References 124 17 Dutch Resolution 125 Richard M. Kellogg CV of Richard M. Kellogg 129 References 129 18 Construction of anti-Me-OH Vicinal Relationships in Polyketides 131 Vaidotas Navickas and Martin E. Maier Introduction 131 Marshall–Tamaru Reaction 131 Conclusions 136 CV of Vaidotas Navickas 136 CV of Martin E. Maier 136 References 136 19 Photoswitchable General Base Catalysts 139 Philipp Viehmann and Stefan Hecht Introduction and Background 139 Strategy and Results 141 Outlook 143 CV of Philipp Viehmann 144 CV of Stefan Hecht 145 References 145 20 Asymmetric Halonium Addition to Olefins 147 Scott A. Snyder and Alexandria P. Brucks Introduction 147 Intramolecular Lactonizations, Etherifications, and Aminations 147 Polyene Cyclizations 150 Intermolecular Additions to Alkenes 150 Conclusion 152 CV of Scott A. Snyder 154 CV of Alexandria P. Brucks 154 References 154 21 Catalytic Asymmetric Gosteli–Claisen Rearrangement (CAGC) 157 Julia Rehbein and Martin Hiersemann CV of Julia Rehbein 162 CV of Martin Hiersemann 162 References 162 22 Biomimetic Total Synthesis of the Penifulvin Family 165 Tanja Gaich and Johann Mulzer Introduction 165 The Penifulvin Family: Isolation and Biogenetic Origin 166 Total Syntheses of Penifulvins A, B, and C 168 Summary 175 CV of Prof. Johann Mulzer 175 CV of Tanja Gaich 175 References 176 23 Catalyst-Controlled 1,3-Polyol Syntheses 179 Tobias Harschneck and Stefan F. Kirsch CV of Stefan F. Kirsch 184 CV of Tobias Harschneck 184 References 185 24 Enantioselective Carbonyl Allylation and Crotylation from the Alcohol Oxidation Level via C–C Bond Forming Transfer Hydrogenation 187 Joseph Moran and Michael J. Krische Introduction and Background 187 Strategy 187 Results 188 CV of Michael Krische 190 CV of Joseph Moran 191 References 195 25 Stereoselective Synthesis with Hypervalent Iodine Reagents 197 Umar Farid and Thomas Wirth CV of Umar Farid 201 CV of Thomas Wirth 201 References 202 26 Asymmetric Gold-Catalyzed Reactions 205 N´uria Huguet and Antonio M. Echavarren Introduction 205 Diphosphine-Gold Complexes in Enantioselective Catalysis 205 Monophosphine-Gold Complexes in Enantioselective Catalysis 208 CV of N´ uria Huguet 209 CV of Antonio M. Echavarren 210 References 210 27 Asymmetric Catalysis in the Total Synthesis of Lipids and Polyketides 213 Santiago Barroso and Adriaan J. Minnaard Background 213 Tuberculostearic Acid: One Isolated Methyl Group 213 Ant Pheromones: Vicinal Methyl Branches 214 Deoxypropionates: 1,3-Methyl Arrays 215 Membrane-Spanning Lipids: 1,4-Dimethyl Units 215 Saturated Isoprenoids: 1,5-Methyl Arrays 217 CV of Santiago Barroso 218 CV of Adriaan J. Minnaard 218 References 218 28 The Evolving Role of Biocatalysis in Asymmetric Synthesis 221 M´elanie Hall, Wolfgang Kroutil, and Kurt Faber Background – First- and Second-Generation Biotransformations 221 Results–Third-Generation Biotransformations 221 a) Asymmetric Bioreduction of C=C Bonds 221 b) Asymmetric Transamination 226 Conclusions and Future Perspectives 228 CV of M´elanie Hall 229 CV of Wolfgang Kroutil 229 CV of Kurt Faber 229 References 229 29 Bifunctional Thiourea Catalysts 233 Yoshiji Takemoto and Tsubasa Inokuma Background 233 Results 233 a) Aminothiourea 233 b) Hydroxythiourea 235 CV of Yoshiji Takemoto 236 CV of Tsubasa Inokuma 237 References 237 30 Catalytic Asymmetric (4 + 3) Cycloadditions Using Allenamides 239 Yun-Fei Du and Richard P. Hsung Introduction and Background 239 Strategy 240 Results 240 Conclusion 242 CV of Yun-Fei Du 246 CV of Richard P. Hsung 246 References 246 31 Application of the Achmatowicz Rearrangement for the Synthesis of Oligosaccharides 249 Michael F. Cuccarese and George A. O’Doherty Introduction 249 De novo Approach to Carbohydrates 249 An Iterative Pd-Catalyzed Glycosylation and Bidirectional Postglycosylation 251 Application to the Synthesis of the Anthrax Tetrasaccharide 251 CV of Michael F. Cuccarese 255 CV of George A. O’Doherty 258 References 258 32 Asymmetric C–C Bond Formation Using Chiral Phosphoric Acid 261 Takahiko Akiyama Background 261 Results 261 a) Mannich and Related Reactions 261 b) Cycloaddition Reactions 262 c) Transfer Hydrogenation Reactions 263 d) Friedel-Crafts Alkylation Reaction 264 e) Desymmetrization reaction 264 Conclusions and Future Perspectives 265 CV of Takahiko Akiyama 266 References 266 33 Asymmetric C–H Bond Functionalization 267 Masayuki Wasa, Kelvin S. L. Chan, and Jin-Quan Yu Background 267 Results 267 a) Diastereoselective C–H Functionalization 267 b) Enantioselective C–H Functionalization 269 Conclusions and Future Perspectives 271 CV of Masayuki Wasa 271 CV of Kelvin S. L. Chan 272 CV of Jin-Quan Yu 272 References 272 34 Asymmetric C–C Bond Formation Using Chiral Guanidine Catalysts 273 Masahiro Terada Background 273 Catalyst Design and Results 273 a) Design of Novel Axially Chiral Guanidine Base Catalysts 273 b) Type I Axially Chiral Guanidine Catalysts (Nine-Membered Ring) 275 c) Type II Axially Chiral Guanidine Catalysts (Seven-Membered Ring) 276 CV of Masahiro Terada 278 References 278 35 Enantioselective Synthesis of Lactones via Rh-Catalyzed Ketone Hydroacylation 279 Matthew M. Coulter and Vy M. Dong Background and Introduction 279 Strategy and Results 279 Conclusions and Future Directions 283 CV of Vy M. Dong 283 CV of Matthew M. Coulter 284 References 284 36 Radical Haloalkylation 285 Armen Zakarian CV of Armen Zakarian 290 References 291 37 Asymmetric Hydrovinylation of Alkenes 293 T. V. (Babu) RajanBabu Introduction 293 New Protocols for the Heterodimerization of Ethylene/Propylene and Vinylarenes, 1,3-Dienes, and Norbornene 293 Catalytic Asymmetric Hydrovinylation Reactions: Effects of Hemilabile Ligands 295 All-Carbon Quaternary Centers via Catalytic Asymmetric HV 295 Hydrovinylation (HV) of 1,3-Dienes and Asymmetric Variations 296 Asymmetric Hydrovinylation of Unactivated Linear 1,3-Dienes Using Co(II) Catalysis 296 Scope and Applications of Hydrovinylation Reactions: Exocyclic Stereocontrol 296 A Stereoselective Route to either Steroid-C20(S) or -C20(R) Derivatives 298 Asymmetric Hydrovinylation of Strained Alkenes 298 Conclusions and Future Perspectives 300 CV of T. V. (Babu) RajanBabu 300 References 301 38 Heterocycle Construction via Asymmetric Rhodium-Catalyzed Cycloadditions 303 Kevin M. Oberg and Tomislav Rovis Background 303 Strategy 304 Results 305 Application to Other Reactions 306 Conclusion and Future Perspectives 307 CV of Tomislav Rovis 307 CV of Kevin M. Oberg 307 References 307 39 N-Heterocyclic Carbene-Catalyzed Aldol Desymmetrizations 309 Karl A. Scheidt, Eric M. Phillips, and Julien Dugal-Tessier Introduction 309 Strategy and Results 309 Application to the Syntheses of Bakkenolides I, J, and S 312 Conclusion 314 CV of Karl A. Scheidt 315 CV of Eric M. Phillips 315 CV of Julien Dugal-Tessier 315 References 316 40 Strategies for the Asymmetric Total Synthesis of Natural Products: ‘‘Chiral Pool’’ versus Chiral Catalysts 317 Karl Gademann Introduction 317 Catalytic Stereoselective Total Synthesis 317 Natural Product Synthesis Starting from Chiral, Nonracemic Starting Materials 320 Conclusion 321 CV of Karl Gademann 321 References 322 41 Dynamic Kinetic Asymmetric Transformations Involving Carbon–Carbon Bond Cleavage 323 Andrew T. Parsons and Jeffrey S. Johnson Background 323 Donor–Acceptor Cyclopropanes as DYKAT Substrates 323 Lewis Acid Catalysis 323 Palladium Catalysis 326 Deracemization of Tertiary Propargyl-Allyl Alcohols via Rhodium-Catalyzed Sequential Rearrangement/Enantioselective Conjugate Addition 329 Conclusion 329 CV of Andrew Parsons 331 CV of Jeffrey Johnson 331 References 331 42 Iron-Catalyzed Allylic Substitutions 333 Markus Jegelka and Bernd Plietker Allylic Substitutions Catalyzed by the Hieber-Anion [Fe(CO)3(NO)]? 333 Allylic Substitutions Catalyzed by Fe2(CO)9 338 CV of Markus Jegelka 340 CV of Bernd Plietker 340 References 341 43 Asymmetric Conia-ene Carbocyclizations 343 Filippo Sladojevich and Darren J. Dixon Introduction and Background: the Conia-ene Reaction 343 Strategy: Organo/Metal Cooperative Catalysis 343 Results 344 CV of Filippo Sladojevich 349 CV of Darren J. Dixon 349 References 350 44 Tactics and Strategies in the Total Synthesis of Chlorosulfolipids 353 Christian Nilewski and Erick M. Carreira Background 353 Stereoselective Synthesis of vic-Dichloride Fragments 353 Total Synthesis of Hexachlorosulfolipid 357 Conclusions 360 CV of Christian Nilewski 360 CV of Erick M. Carreira 360 References 360 45 Linear Free Energy Relationships (LFERs) in Asymmetric Catalysis 363 Elizabeth N. Bess and Matthew S. Sigman Introduction and Background 363 Hammett Electronic Parameters and Their Application to (salen)Mn(III)-Catalyzed Asymmetric Epoxidation Reactions 364 Relating Brønsted Acidity to Enantiomeric Ratio in an Asymmetric Hydrogen-Bond-Catalyzed Diels-Alder Reaction 365 An LFER Describing the Influence of Steric Bulk in a Nozaki–Hiyama–Kishi Asymmetric Allylation of Acetophenone 367 Correlating Quadrupole Moment to Enantioselectivity in Cation-?-Mediated Asymmetric Polycyclization 367 Simultaneously Correlating Hammett and Charton Parameters to Enantioselectivity in Two-Dimensional Free Energy Relationships 368 Conclusions 369 CV of Elizabeth Bess 369 CV of Matt Sigman 369 References 370 46 Asymmetric Diamination of Alkenes 371 Jos´e A. Souto and Kilian Mu˜niz Introduction and Background 371 Strategy 371 Results 371 CV of Jos´e Souto 374 CV of Kilian Mu˜niz 375 References 375 47 Enzymatic Asymmetric Synthesis of Tertiary Alcohols 377 Michael Richter Introduction 377 YerE–a Unique ThDP-Dependent Enzyme 377 Hydroxynitrile Lyases 379 Conclusion 380 CV of Michael Richter 381 References 381 48 Oxidative Dearomatization and Organocatalytic Desymmetrization 383 Alice E. Williamson and Matthew J. Gaunt Introduction 383 Desymmetrization of Cyclohexadienones 383 A One-Pot Oxidative Dearomatization and Catalytic Desymmetrization 384 Oxo- and Aza-Michael Additions 384 Further One-Pot Methods for Oxidative Dearomatization and Catalytic Desymmetrization 386 Alkylative Dearomatization 386 Summary 389 CV of Matthew J. Gaunt 389 CV of Alice E. Williamson 390 References 390 49 Total Synthesis of All (–)-Agelastatin Alkaloids 391 Mohammad Movassaghi and Sunkyu Han Introduction 391 Biosynthetically Inspired Plan for Total Synthesis 391 Total Synthesis of the Agelastatin Alkaloids 393 CV of Mohammad Movassaghi 395 CV of Sunkyu Han 396 References 396 Index 397
Mathias Christmann studied chemistry at the Technical University of Braunschweig and received a PhD from the Leibniz University of Hannover with Markus Kalesse. After a postdoctoral research with Craig J. Forsyth at the University of Minnesota, he started his independent career at the RWTH Aachen as a Liebig-Fellow of the Fonds der Chemischen Industrie. Since 2008, Christmann is an Associate Professor at the Technical University of Dortmund working in the areas of organocatalysis, natural products synthesis and sustainable chemistry. Stefan Brase studied chemistry in Bangor, UK, Marseille, France, and Gottingen, Germany, where he gained his doctorate under Armin de Meijere in 1995. After post-doctoral appointments at Uppsala University, Sweden under J.-E. Backvall and The Scripps Research Institute, La Jolla, USA with K. C. Nicolaou, he began his research career at the RWTH Aachen with Dieter Enders in 1997, obtaining his lecturing qualification in 2001. He became a professor at the University of Bonn that same year and since 2003 he has been Full Professor at the Karlsruhe Institute of Technology. Professor Brase has more than 250 publications to his name and is a recipient of the ORCHEM award. His research interests include methods in drug discovery, combinatorial chemistry with a focus on the synthesis of biologically active compounds, total synthesis of natural products and nanotechnology.
After the overwhelming success of 'Asymmetric Synthesis - The Essentials', narrating the colorful history of asymmetric synthesis, this is the second edition with latest subjects and authors. While the aim of the first edition was mainly to honor the achievements of the pioneers in asymmetric syntheses, the aim of this new edition was bringing the current developments, especially from younger colleagues, to the attention of students. The format of the book remained unchanged, i.e. short conceptual overviews by young leaders in their field including a short biography of the authors. The growing multidisciplinary research within chemistry is reflected in the selection of topics including metal catalysis, organocatalysis, physical organic chemistry, analytical chemistry, and its applications in total synthesis. The prospective reader of this book is a graduate or undergraduate student of advanced organic chemistry as well as the industrial chemist who wants to get a brief update on the current developments in the field.

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