Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1980 Organomercury, -rhodium and -palladium compounds in organic synthesis Susan Smith Hershberger Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Hershberger, Susan Smith, "Organomercury, -rhodium and -palladium compounds in organic synthesis " (1980). Retrospective Theses and Dissertations. 7332. https://lib.dr.iastate.edu/rtd/7332 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS This was produced from a copy of a document sent to us for microfilming. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help you understand markings or notations which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing P3ge(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure you of complete continuity. 2. When an image on the film is obliterated with a round black mark it is an indication that the film inspector noticed either blurred copy because of movement during exposure, or duplicate copy. Unless we meant to delete copyrighted materials that should not have been filmed, you will find a good image of the page in the adjacent frame. 3. When a map, drawing or chart, etc., is part of the material being photo­ graphed the photographer has followed a definite method in "sectioning" the material. It is customary to begin filming at the upper left hand comer of a large sheet and to continue from left to right in equal sections with small overlaps. If necessary, sectioning is continued again—beginning below the first row and continuing on until complete. 4. For any illustrations that cannot be reproduced satisfactorily by xerography, photographic prints can be purchased at additional cost and tipped into your xerographic copy. Requests can be made to our Dissertations Customer Services Department. 5. Some pages in any document may have indistinct print. In all cases we have filmed the best available copy. UniversiV Micrallms International 300 N. ZEEB ROAD, ANN ARBOR. Ml 48106 18 BEDFORD ROW, LONDON WCIR 4EJ, ENGLAND 8012965 HERSHBERGER, SUSAN SMITH ORGANOMERCURY, -RHODIUM AND -PALLADIUM COMPOUNDS IN ORGANIC SYNTHESIS Iowa Stale University PH.D. 1980 University Microfilms In t © r n âti O n â I 300 N. Zeeb Road. Ann Arbor. MI 48106 18 Bedford Row. London WCIR 4EJ. England Organomercury, -rhodium and -palladium compounds in organic synthesis by Susan Smith Hershberger A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Department; Chemistry Major: Organic Chemistry Signature was redacted for privacy. In Charge of Major Work Signature was redacted for privacy. For" bhe Maj pfr Department Signature was redacted for privacy. For the Graduate College Iowa State University Ames, Iowa 1980 ii TABLE OF CONTENTS Page DEDICATION iv QUOTATION V INTRODUCTION 1 PART I: ALKYLATION OF ORGANOMERCURIALS VIA 3 ORGANORHODIUM SPECIES I. ORGANORHODIUM CHEMISTRY PERSPECTIVES 4 II. METHYLATION OF VINYLMERCURIALS: SYNTHESIS 31 OF METHYL-SUBSTITUTED OLEFINS A. Introduction B. Results and Discussion C. Conclusion D. Experimental Section III. METHYLATION OF ARYLMERCURIALS: SYNTHESIS 100 OF METHYL-SUBSTITUTED ARENES A. Introduction 100 B. Results and Discussion 102 C. Conclusion 145 D. Experimental Section 146 IV. VINYL AND ARYL SUBSTITUTION OF ORGANOMERCURIALS 164 A. Introduction 164 B. Results and Discussion 165 C. Conclusion 193 D. Experimental Section 19 4 iii Page V. THE SYNTHESIS OF DIVINYL AND DIARYL KETONES 209 A. Introduction 209 B. Results and Discussion 213 C. Conclusion 240 D. Experimental Section 242 VI. CONCLUSION 2 59 PART II. STABLE ALKYLPALLADIUM COMPOUNDS FROM 263 VINYLMERCURIALS, DJi^ITHIUM TETRACHLORO- PALLADATE AND BICYCLIC OLEFINS I. ORGANOPALLADIUM CHEMISTRY PERSPECTIVES 264 II. SYNTHESIS OF VINYL NORBORNYLPALLADIUM 281 COMPOUNDS, RELATED VINYL ALKYLPALLADIUM COMPOUNDS AND A VINYL NORTRICYCLYLPALLADIUM COMPOUND A. Introduction 281 E. Results and Discussion 2 89 C. Conclusion 331 D. Experimental Section 334 III. CONCLUSION 3 58 BIBLIOGRAPHY 360 ACKNOWLEDGEMENTS 383 iv DEDICATION For Jim V QUOTATION A little Madness in the Spring Is wholesome even for the King, But God be with the clown- Who ponders this tremendous scene- This whole Experiment of Green- As if it were his own! Emily Dickinson 1 INTRODUCTION Organo-transition metal compounds are valuable in organic synthesis both as versatile reagents and reactive inter­ mediates. In addition to their often unique reactivity and selectivity, they may function catalytically. Common methods for forming or elaborating organo-transition metal complexes include: oxidative addition, transmetalation, nucleophilic displacement and insertion reactions. The reverse of oxida­ tive addition, reductive elimination may result in carbon- carbon bond formation and is especially interesting to organic chemists. Currently, these classifications represent synthetic mnemonics rather than precise mechanistic descrip­ tions. In this thesis, the first two modes of organometallic compound formation, oxidative addition and transmetalation are utilized extensively. However, the synthetic implications and applications of these processes and compounds in organic chemistry are emphasized most. This thesis has two main divisions. In Part I, organo- mercury compounds react with organorhodium compounds ulti­ mately resulting in carbon-carbon bond formations and the synthesis of methyl-substituted alkenes and arenes, vinyl and phenyl substituted compounds and divinyl and diaryl ketones. In Part II, stable alkylpalladium compounds are formed from vinyl mercurials, palladium chloride and bicyclic olefins. 2 Although the compounds and their requisite chemistry in Parts I and II are quite different. Parts I and II are not com­ pletely unrelated. In both, transmetalation between a rela­ tively unreactive organomercury compound and a transition metal compound produces a more reactive organo-transition metal compound. Primarily, this thesis further demonstrates both the generality of these transmetalations and their potential role in synthetic organic chemistry. 3 PART I: ALKYLATION OF ORGANOMERCURIALS VIA ORGANORHODIUM SPECIES 4 I. ORGANORHODIUM CHEMISTRY PERSPECTIVES Among Group VIII metals, complexes of rhodium are exten­ sively employed in homogeneous catalysis and the synthesis of organic molecules from inorganic and simple organic reac- tants. A comprehensive review of organorhodium chemistry is completely beyond the scope of this introduction due to both magnitude and diversity. Since this part of the thesis emphasizes organomercury and -rhodium chemistry applied to synthetic organic chemistry, this chapter introduces organo­ rhodium chemistry. A useful perspective of organorhodium chemistry for a synthetic organic chemist might be provided by briefly considering common organorhodium compounds and reactions and subsequently examining carbon-carbon bond forma­ tions facilitated by organorhodium compounds. A common reaction of rhodium compounds is oxidative addition. Oxidative addition is a reaction of coordinatively unsaturated transition metal compounds. The conversion is illustrated (Eq. 1) where M represents a transition compound M + A-B > A-M-B (1) including ancillary ligands and A-B represents a covalent molecule. In this transformation the oxidation state of the metal increases by two. This process is typical of the Group VIII metals: iron, ruthenium, osmium, cobalt, rho­ 5 dium, iridium, nickel, palladium, and platinum. Several reviews have appeared.^ ^ These reviews emphasize the scope of the reaction, discussing a variety of metals, and metal ligand systems, a variety of addends and some mechanistic considerations. The tendency of these metals to undergo oxidative addition increases as one descends a triad and as one moves toward the left of the periodic table. The ligand system also modifies the reactivity of the metal; specifi­ cally, ligands which increase the electron density on the metal facilitate oxidative addition. If the addend is an organic molecule the adduct contains a transition metal- carbon bond of potential utility in organic synthesis for either functionalization or carbon-carbon bond formation. One rhodium compound which is coordinatively unsatu­ rated and undergoes numerous oxidative addition reactions is Wilkinson's catalyst, tris(triphenylphosphine)rhodium chlo­ ride, [PfCgHgjgjgRhCl. Similar rhodium compounds with other aryl, alkyl, or aryl and alkyl phosphine or arsine ligands react analogously and are considered here also. Some of the varied covalent molecules which oxidatively add to these 5-9 complexes include; hydrogen (Eq. 2) and halogens, hydrogen halides (Eq.