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The Carbene/Carbenoid Chemistry of Lithium and Tin Cyclopropylidenoids " (1984)

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The Carbene/Carbenoid Chemistry of Lithium and Tin Cyclopropylidenoids Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1984 The ac rbene/carbenoid chemistry of lithium and tin cyclopropylidenoids Robert D. Herold Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Herold, Robert D., "The carbene/carbenoid chemistry of lithium and tin cyclopropylidenoids " (1984). Retrospective Theses and Dissertations. 8997. https://lib.dr.iastate.edu/rtd/8997 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 reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(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 complete continuity. 2. When an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed. For blurred pages, a good image of the page can be found in the adjacent frame. If copyrighted materials were deleted, a target note will appear listing the pages in the adjacent frame. 3. When a map, drawing or chart, etc., is part of the material being photographed, a definite method of "sectioning" the material has been followed. 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 illustrations that cannot be satisfactorily reproduced by xerographic means, photographic prints can be purchased at additional cost and inserted into your xerographic copy. These prints are available upon request from the Dissertations Customer Services Department. 5. Some pages in any document may have indistinct print. In all cases the best available copy has been filmed. Uni International 300 N. Zeeb Road Ann Arbor, Ml 48106 8423642 Herold, Robert D. THE CARBENE/CARBENOID CHEMISTRY OF LITHIUM AND TIN CYCLOPROPYLIDENOIDS. (VOLUMES I AND II) Iowa State University PH.D. 1984 University IVlicrofilms In t6 rn âîl 0 n â I 300 N. zeeb Road, Ann Arbor, Ml 48106 PLEASE NOTE: In all cases this material has been filmed in the best possible way from the available copy. Problems encountered with this document have been identified here with a check mark V , 1. Glossy photographs or pages 2. Colored illustrations, paper or print 3. Photographs with dark background 4. Illustrations are poor copy 5. Pages with black marks, not original copy 6. Print shows through as there is text on both sides of page 7. Indistinct, broken or small print on several pages / 8. Print exceeds margin requirements 9. Tightly bound copy with print lost in spine 10. Computer printout pages with indistinct print 11. Page(s) lacking when material received, and not available from school or author. .12. Page(s) seem to be missing in numbering only as text follows. 13. Two pages numbered . Text follows. 14. Curling and wrinkled pages 15. Other University Microfilms International The carbene/carbenoid chemistry of lithium and tin cyclopropylidenoids by Robert D. Herold Volume 1 of 2 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. of Major Work Signature was redacted for privacy. For the Major 'apartment Signature was redacted for privacy. For the Graduate College Iowa State University Ames, Iowa 1984 ii TABLE OF CONTENTS Page DEDICATION iv INTRODUCTION 1 I. l-BROMO-l-LITHIO-2-VINyLCYCLOPROPANE DERIVATIVES 4 A. Introduction 4 B. Results and Discussion 15 C. Conclusion 66 D. Experimental 70 II. 7-BROMO-7-LITHIOBICYCLo[4.1.o]-HEPTANE 163 A. Introduction 163 B. Results and Discussion 175 C. Conclusion 194 D. Experimental 198 III. 7-BROMO-7-TRIMETHYLSTANNYLBICYCLO[ 4.1.o]- HEPT-2-ENE 213 A. Introduction 213 B. Results and Discussion 219 C. Conclusion 295 D. Experimental 299 IV. 7-BROMO-7-TRIMETHYLSTANNYLBICYCLO[4.1.O]- HEPTANE 362 A. Introduction 362 B. Results and Discussion 364 iii Page C. Conclusion 414 D. Experimental 419 CONCLUSION 449 REFERENCES 453 ACKNOWLEDGMENTS 462 iv DEDICATION To my loving wife, LuLu 1 INTRODUCTION This introduction will begin with a general discussion of carbene vs. carbenoid reaction mechanisms, paraphrased from the discussion provided by Kirmse.1 The simplest way to visualize a methylene transfer reaction is the unimolecular mechanism shown in equation (1) below. It involves two steps: a) dissociation of the methylene donor (R2CAB) to A-B plus a carbene, and b) reaction of the carbene with a methylene acceptor (Y-Z). RgCCg + RgC: (1) The other mechanistic extreme, shown in equation (2) below, is a bimolecular reaction between the methylene donor and the methylene acceptor, which leads to a concerted, or successive displacement of A and B by the groups Y and Z. R2CC2 + A-B (2) R A-B-C-Y-Z R Very weak bonding of A and B to the carbon in the transition state of the bimolecular reaction minimizes the 2 difference between the unimolecular and bimolecular mechanisms shown in equations (1) and (2), respectively. The term "carbenoid" has been coined to classify such borderline cases of methylene transfer. (A similar gradation of mechanisms can exist between S^l and S^2 reactions in solvolysis studies. In both fields of study, however, the first approximation provided by the unimolecular and bimolecular mechanisms can be quite useful.) A "carbenoid" is an intermediate which exhibits reactions qualitatively similar to those of carbenes, without actually being a free carbene, i.e. a free divalent carbon species. Although a carbene is structurally well defined, a carbenoid usually is not. In the literature, "carbenoid" sometimes refers to a reactive intermediate which undergoes reactions typical of a carbene, but whose precise structure is not certain. In this dissertation, however, "carbenoid" will refer to such an intermediate which is not a free carbene. Chapter I of this dissertation will deal with the 1,3-rearrangement of l-bromo-l-lithio-2-vinylcyclopropanes, in so far as it relates to the 1,3-rearrangement of 2-vinyl- cyclopropylidenes (the so-called "Skattebol rearrange- ment" 2' 3 ). Chapter II will concern itself with the conditions required in order for 7-bromo-7-lithiobicyclo[4.1. o] heptane to generate the corresponding cyclopropylidene. This study 3 relates directly to that conducted in Chapter I in the sense that it explores the question of whether it is reasonable to postulate free carbene intermediates for the rearrangement reactions of l-bromo-l-lithio-2-vinylcyclopropanes. Chapter III will investigate the suitability of 7-bromo-7-trimethyl- stannylbicyclo [4 .1.o] hept-2-ene for a study of the 1,3-rear- rangement of bicyclo [4.1. Q| hept-2-en-7-ylidene. Finally, Chapter IV will reinvestigate the pyrolysis mechanism of 7-bromo-7-trimethylstannylbicyclo [4.1.0] heptane, in an effort to ascertain whether a cyclopropylidene intermediate is really involved. 4 I. l-BROMO-l-LITHIO-2-VINYLCYCLOPROPANE DERIVATIVES A. Introduction The direct rearrangement of carbene 1 to carbene ^ is unique in that the divalent carbon atom retains its integrity. This particular type of carbene rearrangement has been dubbed "type II," as opposed to "type I," in which the divalent carbon of the rearranged carbene is different from that of the unrearranged carbene.^ For simplicity, the 1,3-rearrangement of 2-vinyIcyclopropy1idenes will sometimes be referred to as the "Skattebol rearrangement," because Skattebol 2' 3 discovered this type of reaction. alkyl shift The remainder of this introduction section will describe the various searches for this rearrangement which have employed 1-halo-l-lithiocyclopropane precursors (^) to the cyclopropylidenes (1). a-Haloalkyllithiums like 3 are 5 R. R 1 3 R 2 5 Li Br H 3 often referred to as carbenoids, because they can some­ times undergo reactions typical of the corresponding free carbenes. For simplicity, they are written as monomeric species with purely covalent C-Li and C-Br bonds. First of all, it is well—known that alkyllithium species exist as aggregates in solution. The particular aggregation state involved could conceivably affect the chemistry ob- served for an intermediate like Secondly, 13 C NMR evidence^indicates that the polar structure shown below 6 is actually quite important. This structure helps to explain reactions in which compounds like 3_ suffer bromine dis­ placement by nucleophiles. In fact, it has been suggested,^ on the basis of various experimental results, that carbenoid reactions of a-haloalkyllithiums probably proceed through intermediates which are somewhere between the covalent and ionic extremes pictured below. 5+ ^C—Li < > C: Li / ^ r (covalent) (ionic) In the 1960s,' Skattebol discovered that when dibromides such as £ (Scheme I) are treated with methyllithium, aliénés (^) and cyclopentadienes (£) are formed.
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