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Functionalization of Cyclopalladated Ligands Using Secondary Phosphines and Meta- Chloroperoxybenzoic Acid Jonathan Kukowski

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Functionalization of Cyclopalladated Ligands Using Secondary Phosphines and Meta- Chloroperoxybenzoic Acid Jonathan Kukowski University of North Dakota UND Scholarly Commons Theses and Dissertations Theses, Dissertations, and Senior Projects January 2017 Functionalization Of Cyclopalladated Ligands Using Secondary Phosphines And Meta- Chloroperoxybenzoic Acid Jonathan Kukowski Follow this and additional works at: https://commons.und.edu/theses Recommended Citation Kukowski, Jonathan, "Functionalization Of Cyclopalladated Ligands Using Secondary Phosphines And Meta-Chloroperoxybenzoic Acid" (2017). Theses and Dissertations. 2258. https://commons.und.edu/theses/2258 This Dissertation is brought to you for free and open access by the Theses, Dissertations, and Senior Projects at UND Scholarly Commons. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of UND Scholarly Commons. For more information, please contact [email protected]. FUNCTIONALIZATION OF CYCLOPALLADATED LIGANDS USING SECONDARY PHOSPHINES AND META-CHLOROPEROXYBENZOIC ACID By Jonathan E. Kukowski Bachelor of Arts, University of North Dakota, 2010 Bachelor of Science, University of North Dakota, 2012 A Dissertation Submitted to the Graduate School of the University of North Dakota In partial fulfillment of the requirements for the degree of Doctor of Philosophy Grand Forks, North Dakota December, 2017 PERMISSION Title Functionalization of Cyclopalladated Ligands Using Secondary Phosphines and meta-Chloroperoxybenzoic Acid Department Chemistry Degree Doctor of Philosophy In presenting this dissertation in partial fulfillment of the requirements for a graduate degree from the University of North Dakota, I agree that the library of this University shall make it freely available for inspection. I further agree that permission for extensive copying for scholarly purposes may be granted by the professor who supervised my dissertation work or, in her absence, by the chairperson of the department or the dean of the Graduate School. It is understood that any copying or publication or other use of this dissertation or part thereof for financial gain shall not be allowed without my written permission. It is also understood that due recognition shall be given to me and to the University of North Dakota in any scholarly use which may be made of any material in my dissertation. Signature October 20, 2017 Date iii TABLE OF CONTENTS LIST OF FIGURES .......................................................................................................... vii LIST OF TABLES ............................................................................................................ xii LIST OF CHARTS .......................................................................................................... xiv LIST OF SCHEMES......................................................................................................... xv LIST OF ABBREVIATIONS ......................................................................................... xvii ABSTRACT ..................................................................................................................... xxi CHAPTER I. INTRODUCTION: ADVANCEMENTS IN C–PR2 (R = ALKYL OR ARYL) BOND FORMATION REACTIONS INVOLVING PALLADIUM .................... 1 I.1. Background ........................................................................................................1 I.2. Hydrophosphination Reactions..........................................................................2 I.2.1. Background ........................................................................................ 2 I.2.2. Recent Developments ........................................................................ 3 I.2.3. Catalyst Design .................................................................................. 7 I.3. Stereoconvergent C–P Bond Formation ..........................................................11 I.3.1. Background ...................................................................................... 11 I.3.2. Dynamic Kinetic Resolution for the Synthesis of Axially Chiral Aminophosphines ..................................................................................... 12 I.4. Reaction of Cyclopalladated Complexes .........................................................15 I.4.1 Background ....................................................................................... 15 I.4.2. Reactions with LiPPh2 ..................................................................... 16 I.4.3. Reactions with KPPh2 ...................................................................... 17 iv I.5. Synthesis of P-Heterocycles ............................................................................19 I.5.1. Background ...................................................................................... 19 I.5.2. Intramolecular C–P Bond Formation .............................................. 20 I.5.3. C–P Bond Cleavage Methodologies ................................................ 21 I.6. Conclusions .....................................................................................................24 I.7. Goals of Study……………………………………………………………......26 II. RESULTS AND DISCUSSION .................................................................................. 28 II.1. Reactions of Cyclopalladated Complexes with HPPh2 ..................................28 II.1.1. Background .................................................................................... 28 3 II.1.2. Reactions at the sp C–Pd Bond ...................................................... 29 II.1.4. Mechanistic Considerations ........................................................... 34 II.1.5. Conclusions .................................................................................... 41 II.2. Reactions of Cyclopalladated Complexes with HPR2....................................42 II.2.1. Background .................................................................................... 42 II.2.2. Reactions of CPCs with Electron-Deficient and -Rich Phosphines 43 II.2.3. Reactions of CPCs with Bulky Secondary Phosphines .................. 45 II.2.4. Reactions of CPCs with the Chiral Phosphine HPt-BuPh.............. 51 II.2.5. 31P NMR Spectral Data for Synthesized Compounds .................... 56 II.2.6. X-Ray Crystallographic Analysis of Complex 92d ....................... 58 II.2.7. Conclusions .................................................................................... 61 II.3. Oxygenation of Cyclopalladated Ligands ......................................................62 II.3.1. Background .................................................................................... 62 II.3.2. Reactions of CPCs with m-Chloroperoxybenzoic Acid ................. 64 v II.3.3. Conclusions .................................................................................... 77 III. EXPERIMENTAL SECTION .................................................................................... 78 III.1. General Procedures and Instrumentation ......................................................78 III.2. Preparation of Products from the Reaction of CPCs with Secondary Phosphines ..................................................................................................................79 III.2.1. General Procedure for Phosphination Reactions .......................... 79 III.2.2. Compounds Synthesized from Reactions of CPCs with Secondary Phosphines ................................................................................................ 80 III.2.3. Sample Preparation and Procedures for 31P NMR Monitoring ..... 99 III.3. Preparation of Products from CPCs and m-Chloroperoxybenzoic Acid ......99 III.3.1. General Oxidation Procedure ........................................................ 99 III.3.2. Compounds Synthesized from Oxidation of CPCs with m-CPBA ................................................................................................................. 100 APPENDIX: Spectra and X-Ray Crystallographic Data ................................................ 108 REFERENCES ............................................................................................................... 202 vi LIST OF FIGURES Figure Page 1. Important steric interactions in complex 1...................................................................... 8 2. Simplified reaction pathway of C–P bond formation from heterobiaryl compounds and Me3SiPR2 reported by Ramírez-López and coworkers. .................................................... 15 3. Mechanism for phosphole synthesis proposed by Baba and coworkers. ...................... 22 31 4. Proton-coupled P NMR spectra of CPC 77/HPPh2/Cs2CO3/toluene-d8 reaction mixtures frozen to –95 °C and kept at rt for: a) 10 min. (4.5 equivalents HPPh2), b) 4 h (4.5 equivalents HPPh2), and c) 10 days (2.5 equivalents HPPh2). .................................. 39 5. ORTEP drawing of the molecular structure of complex 92d. Thermal ellipsoids are shown at the 50% probability level. .................................................................................. 59 6. 1H NMR spectrum of iminophosphine 78. ................................................................. 109 7. 31P{1H} NMR spectrum of iminophosphine 78. ......................................................... 110 8. 1H NMR spectrum of µ-chloro--diphenylphosphido complex 79. ........................... 111 31 1 9. P{ H} NMR spectrum of µ-chloro--diphenylphosphido complex 79. .................. 112 1 10. H NMR spectrum of terminal phosphido complex 80
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