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Asymmetric Synthesis II: More Methods and Applications

Asymmetric Synthesis II: More Methods and Applications

Mathias Christmann (Editor), Stefan Bräse (Editor)

ISBN: 978-3-527-67259-2

Apr 2013

430 pages



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 α, β-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 β-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 α, β-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-π-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