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Amino Acid-Based Catalysts for Synthesis of Chiral Amines

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Amino Acid-Based Catalysts for Synthesis of Chiral Amines Amino Acid-Based Catalysts for Synthesis of Chiral Amines Author: Peng Fu Persistent link: http://hdl.handle.net/2345/1528 This work is posted on eScholarship@BC, Boston College University Libraries. Boston College Electronic Thesis or Dissertation, 2009 Copyright is held by the author, with all rights reserved, unless otherwise noted. Boston College The Graduate School of Arts and Sciences Department of Chemistry Amino Acid-Based Catalysts for Synthesis of Chiral Amines a dissertation by Peng Fu Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy August 2009 © Copyright by Peng Fu 2009 Amino Acid-Based Catalysts for Synthesis of Chiral Amines Peng Fu Thesis Advisors: Marc L. Snapper, Amir H. Hoveyda ABSTRACT ¾ Chapter 1. Combinatorial Strategies in Asymmetric Catalysis Review of the Asymmetric Catalysis Methodology Developed in Peptide Project ¾ Chapter 2. Catalytic Asymmetric Alkylations of Ketoimines Zr-Catalyzed Additions of Dialkylzinc Reagents to Aryl-, Alkyl-, and Trifluoroalkyl-Substituted Ketoimines MeO MeO OMe OMe N N Zr-Peptide Complex alkyl NH alkyl NH OMe or +(alkyl)2Zn or R R CF OMe 3 R R CF3 O O R = aryl, alkyl R = aryl R=aryl, alkyl R = aryl ¾ Chapter 3. Ag-Catalyzed Asymmetric Vinylogous Mannich Reactions Asymmetric Vinylogous Mannich Reactions with γ-Substituted Siloxyfurans Asymmetric Vinylogous Mannich Reactions with Siloxypyrroles G = H or OMe MeS MeS OMe MeS G Ag-Peptide Complex HN HN N + or or Me OTMS N OTMS O Boc R R R H Me O BocN O O ¾ Appendix. Catalytic Enantioselective Imine Allylation Ag-Catalyzed Additions of Allyl Boronates to Aldimines and Ketoimines MeS MeS SMe SMe Ag-Peptide Complex N or N O NH or NH + OMe B OMe R H R O R H R O O Table of Contents Chapter 1 Combinatorial Strategies in Asymmetric Catalysis Contents Page Abstract 1 1.1 Early Examples of Applications of Combinatorial Strategy in Asymmetric Catalysis 3 1.2 Review of the Asymmetric Catalysis Methodology Developed from the Hoveyda/Snapper 8 Collaboration Initial Exploration in Development of Peptide Catalyst for Asymmetric Catalysis 8 Asymmetric Addition to Carbonyl Group 10 Asymmetric Addition to Imine Group 13 Asymmetric Conjugate Addition 32 Asymmetric Allylic Alkylation 46 Organocatalysis 54 1.3 Conclusion and Outlook 59 Chapter 2 Catalytic Asymmetric Alkylations of Ketoimines Enantioselective Synthesis of N-Substituted Quaternary Stereogenic Carbon Centers by Zr-Catalyzed Additions of Dialkylzinc Reagents to Aryl-, Alkyl- and Trifluoroalkyl-Substituted Ketoimines Contents Page Abstract 60 2.1 Importance of Chiral Amines Bearing N-Substituted Quaternary Carbons 61 2.2 Non-Catalytic Methods for the Synthesis of Chiral Amines Bearing N-substituted 62 Quaternary Carbons 2.3 Catalytic Methods for the Synthesis of Chiral Amines Bearing N-Substituted Quaternary 64 Carbons 2.4 Catalytic Asymmetric Additions of Organometallic Reagents to Pro-chiral Aldimines 69 2.5 Dialkylzinc Reagents’ Characteristics, Structure and Synthesis 74 2.6 Summary of Previous Contributions 76 2.7 Synthesis of Aryl-Substituted α-Ketoimine Esters and Aryl-Substituted Trifluoromethyl 77 Ketoimines 2.8 Catalytic Asymmetric Alkylations (AA) of Aryl-Substituted α-Ketoimine Esters with 78 Me2Zn 2.9 Catalytic Asymmetric Alkylation (AA) Reactions of Aryl-Substituted α-Ketoimine Esters 86 with Et2Zn 2.10 Catalytic Asymmetric Alkylation (AA) Reactions of Aryl-Substituted α-Ketoimine Esters 91 with other Dialkylzinc Reagents 2.11 Catalytic Asymmetric Alkylation (AA) Reactions of Aryl-Substituted Trifluoromethyl 92 Ketoimines 2.12 Synthesis of Alkyl-Substituted α-Ketoimine Esters 95 2.13 Identification of an Optimal Chiral Ligand for Catalytic Asymmetric Alkylation (AA) 97 Reactions of Alkyl-Substituted α-Ketoimine Esters 2.14 Catalytic Asymmetric Alkylation (AA) Reactions of Alkyl-Substituted α-Ketoimine 98 Esters 2.15 Studies on the Practical Utility of Zr-Catalyzed AA Reactions 99 2.16 Removal of the N-aryl group 101 2.17 Functionalization of α-Quaternary Amino Esters obtained through Zr-Catalyzed AA 102 Reactions 2.18 Mechanistic Models 103 2.19 Conclusion 105 Chapter 3 Ag-Catalyzed Enantioselective Vinylogous Mannich (AVM) Reactions of Siloxypyrroles and γ-Substituted Siloxyfurans Contents Page Abstract 107 3.1 Mannich Reaction and Synthetic Applications 108 3.2 Catalytic Asymmetric Mannich Reactions 111 Catalytic Asymmetric Mannich Reactions Utilizing Preformed Enolates 111 Direct Catalytic Asymmetric Mannich Reactions 115 Catalytic Asymmetric Mannich Reactions to Generate Quaternary Carbon Center 124 3.3 Ag Complex Catalyzed Asymmetric Mannich Reactions 126 3.4 Furan-, Pyrrole- and Thiophene-Based Siloxydienes 130 Synthesis of Higher Carbon Sugars and Azasugars 130 Synthesis of Tetrahydrofuran Derivatives 132 Synthesis of Pyrrolizidine, Indolizidine and Quinolizidine Alkaloids 132 3.5 π-Nucleophilicity of Silyl Enol Ethers 134 3.6 Asymmetric Vinylogous Mannich Reactions with γ-Substituted Siloxyfurans 134 3.7 Initial Results for AVM Reactions with γ-Substituted Siloxyfurans 135 3.8 Protecting Group Manipulation for AVM Reactions with γ-Substituted Siloxyfurans 140 3.9 Initial Studies on Catalytic AVM Reactions with Siloxypyrroles 146 3.10 Protecting Group Manipulation for AVM Reactions with Siloxypyrrole 3.55 149 3.11 Exploration of Substrate Scope for AVM Reactions with Siloxypyrrole 3.55 152 3.12 Application of ortho-Thiomethyl-para-methoxyaniline in Three- component Catalytic 157 AVM Reactions of alkyl-Substituted Aldimines 3.13 Application of ortho-Thiomethyl-para-methoxyaniline in Enantioselective 159 Aza-Diels-Alder Reactions of alkyl-Substituted Aldimines and Danishefsky Diene 3.14 Removal of ortho-Thiomethyl-para-methoxyaniline Protecting Group 160 3.15 Proposed Mechanistic Working Models 160 3.16 Conclusion and Future Plan 161 Appendix Ag-Catalyzed Enantioselective Imine Allylation with Allyl Boronates Contents Page Abstract 163 4.1 Asymmetric Allylation of Imines Involving Allyl Boronates 164 4.2 Initial mono-Amino Acids Peptide Ligand Screen for Asymmetric Imine Allylation 167 4.3 di-Peptide Ligand Screen for Asymmetric Imine Allylation 167 N-Terminus Screen on di-Peptide Ligand for Asymmetric Imine Allylation 167 AA1 Amino Acids Screen on di-Peptide Ligand for Asymmetric Imine Allylation 170 AA2 Amino Acids Screen on di-Peptide Ligand for Asymmetric Imine Allylation 170 4.4 Modification on Other Reaction Conditions 171 Solvent Screen for Asymmetric Imine Allylation 171 Temperature Study for the Asymmetric Imine Allylation 172 Time and Catalyst Loading Study for Asymmetric Imine Allylation 173 4.5 Lewis Acid Screen for Asymmetric Imine Allylation 174 4.6 New Ligand Development for Asymmetric Imine Allylation 176 4.7 Asymmetric Ketoimine Allylation 176 Attachment (Experimental Section and Supporting Information) Contents Page Publication Part I Experimental Section and Supporting Information for Chapter 2 Part II Experimental Section and Supporting Information for Chapter 3 Part III List of Abbreviations Å Angström AA1 Amino acid 1 AA2 Amino acid 2 Ac2O Acetic anhydride AcOH Acetic acid Ala Alanine Ald Aldehyde Al2O3 Alumina gel Anal Elemental analysis Ar Aryl aq Aqueous AVM Asymmetric Vinylogous Mannich BF3•Et2O Boron trifluoride diethyl etherate BINAP 2,2’-Bis(diphenylphosphino)-1,1’-binaphthyl BINOL 1,1’-Bi-2-naphthol Boc N-tert-butoxycarbonyl Boc2O di-tert-butyl-dicarbonate Bn Benzyl br Broad (spectroscopy) Bu Butyl n-BuOH n-Butanol C Celsius c Concentration (weight / volumn) for optical rotation calcd Calculated CAN Ceric(IV) ammonium nitrate CBZ N-carbobenzyloxy CH2Cl2 Methylene chloride (dichloromethane) Chg Cyclohexylglycine cm-1 Wavenumbers CN Cyanide COD 1,5-cyclooctadiene config Configuration conv Conversion C-term carboxy terminus of an amino acid or peptide Cy Cyclohexyl δ NMR scale (chemical shift) d doublet ∆ heat o degree DCE 1,2-dichloroethane DNA Deoxyribonucleic acid DMAP 4-(dimethylamino)pyridine DMF N,N-dimethylformamide DMSO dimethylsulfoxide EDC 1-(N,N-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride ee enantiomeric excess Et Ethyl Et3N Triethylamine Enz Enzyme Et2O Diethyl ether EtOAc Ethyl acetate eq equation equiv equivalents FMOC N-(9-fluorenylmethoxycarbonyl) g gram GC Gas chromatography Gly Glycine h hour HBTU O-benzotriazole-N,N,N’,N’-tetramethyl-uronium-hexafluoro-phosphate HMPA Hexamethylphosphoramide HOBt N-hydroxybenzotriazole monohydrate HOi-Pr isopropanol HPLC High performance liquid chromatography HTS High throughput screening hυ light Hz hertz IC50 Concentration at which inhibition is 50% Ile Isoleucine IR Infrared spectroscopy k Reaction rate constant kcal kilocalorie L liter λ wavelength LDA Lithium diisopropylamide t-Leu tert-Leucine LUMO Lowest unoccupied molecular orbital M Molarity (concentration mol / L) m Multiplet m meta mCPBA 3-chloroperbenzoic acid Me Methyl MeCN Acetonitrile MeNO2 Nitromethane MeOH Methanol Met Methionine mg milligram MHz Megahertz min minute mmol millimole mL milliliter mol mole MP Melting point 2-Nal 2-Naphthalanine NHAc Acetamide nm nanometer NMR Nuclear magnetic resonance N-term Nitrogen terminus of an amino acid or peptide Nu Nucleophile o ortho OAc Acetate p para p pentet % percent Ph Phenyl PhCHO Benzaldehyde Phe Phenylalanine Phg Phenylglycine PhH Benzene PhMe Toluene PhI(OAc)2 Iodobenzene diacetate ppm parts per million q Quartet rac racemic rt Room temperature s Singlet satd Saturated SB Schiff base SiO2 Silica gel t Triplet TBAF tetra-butyl ammonium fluoride TBS tert-butyldimethylsilyl TBTU O-benzotrazole-N,N,N’,N’-tetramethyl-uronium-tetrafluro-borate
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