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Preparation of Allylic Ketones Via Acylation of Allylic Mercurials ; And

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Preparation of Allylic Ketones Via Acylation of Allylic Mercurials ; And Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1991 Preparation of allylic ketones via acylation of allylic mercurials ; and, Palladium(0)-catalyzed coupling of aryl iodides, nonconjugated dienes, and nucleophiles Yong-de Lu Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Lu, Yong-de, "Preparation of allylic ketones via acylation of allylic mercurials ; and, Palladium(0)-catalyzed coupling of aryl iodides, nonconjugated dienes, and nucleophiles " (1991). Retrospective Theses and Dissertations. 9660. https://lib.dr.iastate.edu/rtd/9660 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]. UMI MICROFILMED 1992 INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMI films the text directly fi-om the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand corner and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. University Microfilms International A Bell & Howell Information Company 300 North Zeeb Road, Ann Arbor, Ml 48106-1346 USA 313/761-4700 800/521-0600 Order Number 9212168 Preparation of allylic ketones via acylation of allylic mercurials and palladium(0)-catalyzed coupling of aryl iodides, nonconjugated dienes, and nucleophiles Lu, Yong-de, Ph.D. Iowa State University, 1991 UMI 300N.ZeebRd. Ann Aibor, MI 48106 Preparation of allylic ketones via acylation of allylic mercurials and Palladium(0)-catalyzed coupling of aryl iodides, nonconjugated dienes, and nucleophiles by Yong-de Lu 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 Approved: Signature was redacted for privacy. In Charge of Major Work Signature was redacted for privacy. W the Major Department Signature was redacted for privacy. For the^pfaduate College Iowa State University Ames, Iowa 1991 u TABLE OF CONTENTS Page GENERAL INTRODUCTION 1 PART I. PREPARATION OF ALLYLIC KETONES VIA ACYLATION OF ALLYLIC MERCURIALS 2 INTRODUCTION 3 PREPARATION OF ALLYLIC MERCURIC IODIDES 14 PREPARATION OF ALLYLIC KETONES 25 CONCLUSION 32 EXPERIMENTAL SECTION 33 REFERENCES 42 PART n. PALLADIUM(0)-CATALYZED COUPLING OF ARYL IODIDES, NONCONJUGATED DIENES, AND NUCLEOPHILES 46 SECTION I. PALLADIUM(0)-CATALYZED COUPLING OF ARYL IODIDES, NONCONJUGATED DIENES, AND CARBON NUCLEOPHILES 46 INTRODUCTION 47 COUPLING OF PHENYL IODIDE, 1,5-HEXADIENE AND DIETHYL MALONATE 58 COUPLING OF ARYL IODIDES, NONCONJUGATED DIENES, AND CARBON NUCLEOPHILES 67 CONCLUSION 78 EXPERIMENTAL SECTION 79 REFERENCES 93 SECTION n. PALLADIUM(0)-CATALYZED COUPLING OF ARYL IODIDES, NONCONJUGATED DIENES, AND HETEROATOM NUCLEOPHILES 96 INTRODUCTION 97 iii Page COUPLING INVOLVING NITROGEN NUCLEOPHILES 108 COUPLING INVOLVING OXYGEN NUCLEOPHILES 127 CONCLUSION 140 EXPERIMENTAL SECTION 141 REFERENCES 158 SECTION in. SYNTHESIS OF PYRIDINE ALKALOŒ) ANALOGUES VIA PALLADIUM(0)-CATALYZED COUPLING OF ARYL lODD^ES, NONCONJUGATED DENES, AND NITROGEN NUCLEOPHILES 161 INTRODUCTION 162 RESULTS AND DISCUSSION 166 CONCLUSION 178 EXPERIMENTAL SECTION 179 REFERENCES 187 GENERAL SUMMARY 188 ACKNOWLEDGMENTS 189 1 GENERAL INTRODUCTION The dissertation consists of two parts made up of a total of four papers suitable for publication in ajournai. The first part of this dissertation discusses the acylation of allylic mercurials by acyl chlorides promoted by aluminum chloride. A variety of allylic mercurials and acyl chlorides can be employed successfully in this reaction. This reaction provides a convenient route to allylic ketones. A modified literature procedure to prepare allylic mercuric iodides from the corresponding allylic halides and metallic mercury is also presented in this part. The second part of this dissertation discusses the palladium-catalyzed coupling of aryl iodides, nonconjugated dienes, and nucleophiles, which generates more than one carbon- carbon bond or carbon-heteroatom bond at a time via palladium migration chemistry. The second part of this thesis is divided into three sections. The first section deals with the palladium-catalyzed coupling of aryl iodides and nonconjugated dienes using carbon nucleophiles. The reaction results in a high degree of regioselectivity and stereoselectivity. Applications of nitrogen and oxygen nucleophiles in this unique coupling reaction are reported in the second section. A variety of amines and the azide anion have been used as representative nitrogen nucleophiles and only one regio- and stereoisomer is isolated in good yields. When oxygen nucleophiles, such as acetate anion and phenoxide anion, are used in the coupling process, a mixture of regio- and stereoisomers is obtained. The focus of the third section is the application of the three-component coupling methodology to the synthesis of analogues of some naturally occurring pyridine alkaloids. The palladium-catalyzed coupling-migration approach is the key step and the total synthesis is accomplished in only two steps. A general summary comes after the four papers. 2 PART 1. PREPARATION OF ALLYLIC KETONES VIA ACYLATION OF ALLYUC MERCURIALS 3 INTRODUCTION The use of organometallic compounds for the synthesis of ketones has been known for more than a century.1 Over the past several decades, reactions involving electrophilic acylation of organometallics to form ketones have been well studied and reviewed.2.3 Organometallic derivatives of aluminum, boron, cadmium, copper, iron, lead, magnesiimi, mercury, nickel, rhodium, silicon, sodium, tin, zirconium, and zinc have been shown to react with acid halides to yield ketones, in some cases catalyzed by a palladium compound. These reactions can be represented by the general equation 1.2.4 O O l" 9 l" 9 R^CX + R^M ^ R^CR2 + MX (1) In this introduction, no effort has been made to cover the literature on the acylation of organometallics reported before 1987, except mercury, since an excellent book^ covering this subject is available. An attempt has been made to cover all primary literature related to the application of organometallics to the synthesis of ketones via acylation through 1990. Included are organometallics of copper, magnesium, titanium, thallium, and zinc, which will be discussed first. Then, the acylation of organomercurials, particularly aUylic mercurials, will be examined in detail. Copper reagents have proven to be very useful in organic synthesis.^ Their synthetic utility would be enhanced further if highly funcdonalized copper compounds could be prepared. Rieke and co-workers have reported that highly reactive copper can be prepared by the lithium naphthalide reduction of the complex copper(I) iodide/triphenylphosphine. This copper reacts with functionalized alkyl halides to give organocopper reagents which can be effectively trapped with acid chlorides to give functionalized ketones in good yields (eq 2).^ 4 Ester, nitrile, chloride, remote epoxide, and, to some extent, ketone groups can be tolerated by this approach, because the preparation of the copper reagent does not involve an organolithium Br(CH,)„Y _PhÇOÇL_ pJ(CH,).Y (2) Y = Cl, COgEt, CN n = 2-7 60-80% COŒ3 4 19% O 6 58% / \ 1-2 0% or Grignard reagent. It is noted that epoxide functionality must be located in such a position that intramolecular epoxide attack by the organocopper species cannot occur. Anyway, this methodology increases the utility of organocopper reagents for ketone synthesis. Knochel et al.^ have found that a new class of highly functionalized copper reagents RCu(CN)ZnI can be prepared by the reaction of a soluble copper salt CuCN* 2LiX (X = CI, Br) with various zinc organometallics (eq 3). Meanwhile, Gaudemar^ developed a mild = n-Bu, /-Pr, cyclohexyl, Et02C(CH2)3, NC(CH2)3 81-94% = n-CsHii, cyclohexyl, Ph synthesis of polyfunctional zinc organometallics by treating various functionalized iodides with activated zinc in TEîF. The copper reagents react rapidly with acid chlorides and furnish the ketones in high yields (see eq 3). Under the standard conditions, the copper
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