Copper(I)-Catalyzed Stereoselective Borylation Reactions: Multisubstituted Alkenyl and Allylic Boronates

Description

This book focuses on the development of novel functionalized organoboron compounds and those synthetic methods. High degrees of chemo-, regio-, and stereoselectivities of the borylation reactions are attained through catalyst design and optimization. Furthermore, the selectivity-determining mechanisms are analyzed with state-of-the-art DFT and other computational methods. In this book, the author synthesizes some multi-substituted alkenyl and allylic boronates via borylation reactions using a copper(I)/diboron catalyst system. Those compounds contain novel densely substituted and distorted structures, which have not been accessed by other methods. The high stereoselectivities are achieved by the optimization of the catalyst, especially the ligand. Some new ligands are also developed in this book. Furthermore, the derivatization of the borylation products is demonstrated to access the sterically demanding complex molecules. Also, the author performs computational analysis to reveal how the catalyst controls the selectivities. The deep insight into the reaction mechanism provides guides for rational catalyst design for not only copper(I) catalysis but also other transition metal catalysis. Thus, the content should be of interest to academic and industrial scientists in a wide range of areas. Cover Springer Theses Series Copper(I)-Catalyzed Stereoselective Borylation Reactions: Multisubstituted Alkenyl and Allylic Boronates Copyright Supervisor’s Foreword List of Publications Acknowledgements Contents 1. General Introduction 1.1 Organoboron Compounds 1.2 Borylation Reactions of Organic Molecules 1.3 Copper(I)-Catalyst/Diboron System for Borylation Reactions 1.4 Characterization of Boryl Copper(I) Species 1.5 Overview References 2. Modification of QuinoxP*-Type Bisphosphine Ligands for High-Performance Asymmetric Boryl Substitution of Racemic Allyl Electrophiles 2.1 Introduction 2.2 Results and Discussion 2.3 Conclusions 2.4 Experimental Details 2.4.1 Instrumentation and Chemicals 2.4.2 General Experimental Procedure 2.4.3 Substrate Preparation Procedure 2.4.4 Borylation Product Characterization 2.4.5 One-Pot Borylation/Allylboration Procedure 2.4.6 Leaving Group Effect 2.4.7 Large-Scale Borylation Reaction 2.4.8 Deuterium Labeling Study 2.4.9 Asymmetric Allylic Boryl Substitution of an Achiral Allyl Carbonate 2.5 Computational Details 2.5.1 Computational Methods and Software Libraries 2.5.2 Detailed Computational Investigation on Boryl Copper(I) Dimers 2.5.3 Computational Analysis on Enantiodetermining Transition State 2.5.4 Computational Analysis on Conformation of (R,R)-5,8-TMS-QuinoxP* 2.5.5 Calculated Properties of All Structures (Table 2.10) References 3. Allylcopper(I) Isomerization-Enabled Copper(I)-Catalyzed Intramolecular Alkylboration of Terminal Allenes 3.1 Introduction 3.2 Results and Discussion 3.3 Conclusions 3.4 Experimental Details 3.4.1 Instrumentation and Chemicals 3.4.2 General Experimental Procedure 3.4.3 Substrate Preparation 3.4.4 Borylation Product Characterization 3.4.5 Functionalization Procedures of Borylation Products 3.4.6 Protonolysis Experiment of Allylcooper(I) Intermediate 3.5 Computational Details 3.5.1 Isomerization of Allylcopper(I) Intermediates 3.5.2 Energy Diagram of Six-Membered Ring Formation Pathway References 4. Intermolecular Alkylboration of gem-Disubstituted Allenes for Stereoselective Synthesis of Multi-alkylated Allylic Boronates 4.1 Introduction 4.2 Results and Discussion 4.3 Conclusions 4.4 Experimental Details 4.4.1 Instrumentation and Chemicals 4.4.2 Substrate Preparation Procedure 4.4.3 Substrate Characterization 4.4.4 General Borylation Procedure 4.4.5 Borylation Product Characterization 4.4.6 Large Scale Reaction and Synthetic Applications 4.4.7 Procedure of Allylboration Reactions 4.4.8 Evaluation of Accuracy of 13C NMR Analysis 4.4.9 2D NMR Study for Determination of Product Stereochemistry 4.4.10 Alkylboration of Aryl-Substituted Allene 4.4.11 Stoichiometric Reaction 4.4.12 Single-Crystal X-ray Structural Analysis 4.5 Computational Details 4.5.1 Calculation Method Details 4.5.2 DFT Study for the Case of Xantphos Ligand Conditions 4.5.3 Discussion About Ligand Effect 4.5.4 Calculated Properties of All Structures (Table 4.9) References 5. Computational Investigation on Copper(I)-Catalyzed Enantioselective Radical Borylation of Benzyl Halides 5.1 Introduction 5.2 Results and Discussion 5.3 Conclusions 5.4 Computational Details 5.4.1 Calculation Method Details 5.4.2 Non-Covalent Interaction (NCI)-Plot 5.4.3 Calculated Properties and Geometries (Table 5.1) References 6. Summary