Atropisomerism in Asymmetric Organic Synthesis

Challenges and Applications
1. Auflage 2024
ISBN: 978-3-527-35283-8
Verlag: Wiley-VCH GmbH

Buch, Englisch, 352 Seiten, Format (B × H): 172 mm x 245 mm, Gewicht: 856 g

Presents new methodologies, strategies, and unique catalysts emerged in the oxidative heterocoupling area and tackles some everlasting challenges.

Autoren/Hrsg.

Takizawa, Shinobu

Salem, Mohamed S. H.

Fachgebiete

• Naturwissenschaften Chemie Physikalische Chemie Chemische Reaktionen, Katalyse
• Naturwissenschaften Chemie Organische Chemie
• Naturwissenschaften Chemie Chemie Allgemein Pharmazeutische Chemie, Medizinische Chemie

Inhaltsverzeichnis

Preface PART I ATROPOSELECTIVE SYNTHESIS 1 Introduction  1.1. Molecular chirality and atropisomerism 1.2. Atropisomerism in asymmetric organic synthesis1.3. Atropisomerism: Challenges and applications 2 Iron- and Ruthenium-catalyzed Atroposelective Synthesis of Axially Chiral Compounds2.1. Introduction2.2. Oxidative homocoupling of 2-naphthols to BINOL and its derivatives2.3. Oxidative cross-coupling of 2-naphthols to asymmetric BINOLs2.4. Oxidative spirocyclization of 2-naphthols2.5. Conclusion 3 Vanadium-catalyzed Atroposelective Coupling of Arenols and Application in the Synthesis of Polycyclic Heteroaromatics PHAs3.1. Introduction3.2. Chiral vanadium catalysis in homo-coupling of hydroxycarbazoles3.3. Chiral vanadium catalysis in hetero-coupling of hydroxycarbazole with 2-naphthols3.4. Enantioselective synthesis of oxa[9]helicenes via chiral vanadium complex-catalyzed homo-couplings of polycyclic phenols3.5. Enantioselective synthesis of oxaza[7]dehydrohelicenes via chiral vanadium complex-catalyzed hetero-couplings of 3-hydroxycarbazoles and 2-naphthols3.6. Summary and Conclusion 4 Atroposelective Suzuki?Miyaura coupling towards Axially Chiral Biaryls: Mechanistic Insight4.1. Introduction4.2. Mechanism insight of SMC reaction and enantiodetermining step4.3. Asymmetric SMC reaction4.4. Conclusion 5 Organocatalytic Enantioselective Formation of Atropisomers 5.1. Introduction5.2. Aminocatalysis5.3. Brønsted base catalysis5.4. Phase Transfer Catalysis5.5. Chiral Phosphoric Acids5.6. Conclusions 6 Synthesis of Atropisomers via Enantioselective Ring-Opening Reactions6.1. Introduction6.2. Asymmetric ring-opening of biaryl lactones and its derivatives6.3. Asymmetric ring-opening reactions via C-I bond cleavage6.4. Asymmetric ring-opening reactions via C-N and C-P bonds cleavage6.5. Asymmetric ring-opening reactions via C-C and C-Si bonds cleavage6.6. Asymmetric ring-opening reactions via C-O and C-S bonds cleavage6.7. Oriented asymmetric ring-opening via transient pentacyclic metal species6.8. Summary and Conclusions PART II CHALLENGES AND APPLICATIONS 7 Axially Chiral Ligands and Catalysts Derived from Atropisomeric Binaphthyl Structures7.1. Introduction 7.2. Chiral ligands derived from BINOLs7.3. Chiral ligands derived from BINAMs7.4. Chiral ligands derived from NOBINs7.5. Chiral organocatalysts derived from BINOLs7.6. Chiral organocatalysts derived from BINAMs7.7. Chiral organocatalysts derived from NOBINs7.8. Chiral ligands and catalysts derived from other Binaphthyl motifs7.9. Summary and Outlook 8 Multinuclear Zinc Catalysts with Axially Chirality8.1. Pioneering works on BINOL-Zn System8.2. Enantioselective addition reaction of dialkylzinc to aldehydes using BINOL additive8.3. Catalytic asymmetric alkynylation of aldehydes8.4. Catalytic asymmetric Diels-Alder reaction8.5. Catalytic asymmetric epoxidation of enones8.6. Catalytic asymmetric direct Aldol reaction8.7. Catalytic asymmetric iodofunctionalization of alkenes8.8. Conclusions 9 Binaphthyl-based Chiral DMAP Derivatives in Enantioselective Transformations9.1. Introduction9.2. Binaphthyl-based chiral DMAP derivatives9.3. Intramolecular acyl transfer reactions9.4. Intermolecular acyl transfer reactions9.5. Summary and Conclusions 10 Catalytic Atroposelective Oxidative Coupling in Natural Product Synthesis10.1. Introduction10.2. Copper-catalyzed asymmetric oxidative coupling to construct a chiral axis10.3. Vanadium-catalyzed asymmetric oxidative coupling to construct a chiral axis10.4. Enzymatic strategies to synthesize natural products via atroposelective coupling10.5. Conclusion 11 Atropisomerism in Drug Discovery and Development11.1. Introduction11.2. Configuration assignment of atropisomeric drugs11.3. Classification of atropisomeric drugs according to the rotational energy barrier11.4. Analysis of atropisomeric drugs across the pharmaceutical market drugs11.5. Introducing atropisomerism to modulate selectivity11.6. Challenges for atropisomerism within drug discovery11.7. Conclusions

Über Autor(innen)

Shinobu Takizawa is Associate Professor at the Institute of Scientific and Industrial Research (SANKEN) and AI Research Center at Osaka University (Japan). He received his Ph.D. in chemistry at the Graduate School of Pharmaceutical Science, Osaka University in 2000. From 2006 to 2008 he did postdoctoral studies at The Scripps Research Institute (USA) with Professor Dale L. Boger. He received the Daiichi Pharmaceutical Co. Ltd. Award in Synthetic Organic Chemistry, Japan (2000), the Pharmaceutical Society of Japan Award for Young Scientists (2009), the Daiichi-Sankyo Co. Ltd. Award in Synthetic Organic Chemistry, Japan (2009), the Osaka University Presidential Award for Encouragement in Research (2015) and the Pharmaceutical Society of Japan Award for Divisional Scientific Promotion (2019). His current research interest focuses on developing sustainable synthetic reactions with machine learning optimization. He is the author of more than 125 articles.Mohamed Salem is a research associate at the Institute of Scientific and Industrial Research at Osaka University. He graduated from the Faculty of Pharmacy, Suez Canal University (Egypt) in 2017, and received his Ph.D. in chemistry at the Graduate School of Science, Osaka University in 2022 under the direction of Professor Hiroaki Sasai and Professor Takayoshi Suzuki. Mohamed was awarded the Japanese Government Scholarship (MEXT) in 2019. His current research interest is designing and synthesizing CPL-responsive SOMs using electrochemistry, machine-learning-assisted optimization of reaction parameters, and asymmetric catalysis.