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The Double [3+2] Photocycloaddition Reaction PDF

199 Pages·2011·1.71 MB·English
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Springer Theses Recognizing Outstanding Ph.D. Research For furthervolumes: http://www.springer.com/series/8790 Aims and Scope The series ‘‘Springer Theses’’ brings together a selection of the very best Ph.D. theses from around the world and across the physical sciences. Nominated and endorsed by two recognized specialists, each published volume has been selected for its scientific excellence and the high impact of its contents for the pertinent fieldofresearch.Forgreateraccessibilitytonon-specialists,thepublishedversions includeanextendedintroduction,aswellasaforewordbythestudent’ssupervisor explaining the special relevance of the work for the field. As a whole, the series will provide a valuable resource both for newcomers to the research fields described, and for other scientists seeking detailed background information on specialquestions.Finally,itprovidesanaccrediteddocumentationofthevaluable contributions made by today’s younger generation of scientists. Theses are accepted into the series by invited nomination only and must fulfill all of the following criteria • They must be written in good English. • The topic should fall within the confines of Chemistry, Physics and related interdisciplinary fields such as Materials, Nanoscience, Chemical Engineering, Complex Systems and Biophysics. • The work reported in the thesis must represent a significant scientific advance. • Ifthethesisincludespreviouslypublishedmaterial,permissiontoreproducethis must be gained from the respective copyright holder. • They must have been examined and passed during the 12 months prior to nomination. • Each thesis should include a foreword by the supervisor outlining the signifi- cance of its content. • The theses should have a clearly defined structure including an introduction accessible to scientists not expert in that particular field. Jason A. Woolford The Double [3+2] Photocycloaddition Reaction Doctoral Thesis accepted by University of Sussex, UK 123 Author Supervisors Dr. JasonA.Woolford Prof.Dr. P.J.Parsons Department of Chemistry Department of Chemistry Universityof Sussex Universityof Sussex Lewes Road Lewes Road Falmer, Brighton Falmer, Brighton BN1 9QJ BN1 9YJ UK UK e-mail: [email protected] e-mail: [email protected] Dr. Clive S.Penkett Department of Chemistry School ofLife Sciences Universityof Sussex Falmer, Brighton,East Sussex BN1 9QJ UK ISSN 2190-5053 e-ISSN 2190-5061 ISBN 978-3-642-22859-9 e-ISBN978-3-642-22860-5 DOI 10.1007/978-3-642-22860-5 SpringerHeidelbergDordrechtLondonNewYork (cid:2)Springer-VerlagBerlinHeidelberg2011 Thisworkissubjecttocopyright.Allrightsarereserved,whetherthewholeorpartofthematerialis concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broad- casting,reproductiononmicrofilmorinanyotherway,andstorageindatabanks.Duplicationofthis publicationorpartsthereofispermittedonlyundertheprovisionsoftheGermanCopyrightLawof September 9, 1965, in its current version, and permission for use must always be obtained from Springer.ViolationsareliabletoprosecutionundertheGermanCopyrightLaw. Theuseofgeneraldescriptivenames,registerednames,trademarks,etc.inthispublicationdoesnot imply, even in the absence of a specific statement, that such names are exempt from the relevant protectivelawsandregulationsandthereforefreeforgeneraluse. Coverdesign:eStudioCalamar,Berlin/Figueres Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Parts of this thesis have been published in the following journal articles: 1. Penkett CS, Woolford JA, Day IJ, Coles MP (2010) The double [3+2] photo- cycloaddition reaction. J Am Chem Soc 132:4–5 2. Penkett CS, Woolford JA, Read TW and Kahan RJ (2011) Investigating the arenyl-diene double [3+2] photocycloaddition reaction. J Org Chem 76: 1295–1304 v Supervisor’s Foreword It is with the greatest of pleasure that I introduce Dr. Jason Woolford’s work for publication in the Springer Theses series. Upon completion of his undergraduate studies in the Chemistry Department at the University of Sussex, Jason was awardedtheprizeforthebestfinalyearMChemprojectandelectedtoworkwith me on the development of novel photochemically mediated transformations. He began his doctoral studies in October 2007 by investigating intramolecular meta photocycloaddition reactions of arenyl dienes. His dedication to practical excel- lence and tenacious attention to detail led to the discovery of the double [3+2] photocycloaddition reaction early on in his D.Phil. studies. This remarkable reaction generatesfourcarbon–carbon bonds, fivenewringsanduptonine chiral centres, which might be a record for a non-cascade process. It has enormous potentialfromtheperspectiveofgreenchemistryandstepeconomy foritsability tocreatemolecularcomplexityusinglightasafacilitator.Thefenestraneproducts thatarereadilyformedbythisprocesshavehugeuntappedpotentialascompounds of biological interest due to their rigid structures. Fenestranes, named so for their windowpane-likeappearancewithfourringssharingacommoncarbonatom,have interestingpropertiesduetotheexceptionallylargebondangleoftheircentralsp3 carbonatom(inthiscase128.5(cid:3)).TheresultsofJason’sresearchendeavourshave beenreportedmorewidelyintheJournaloftheAmericanChemicalSociety(2010, 132, 4) as a communication and in the Journal of Organic Chemistry (2011, 76, 1295) as an article. This chemistry has received much international acclaim with theoriginalcommunicationbeingoneofthetwentymost-readpapersinthemonth followingitspublication.Wehopethatthescientificcommunitywillbuildonour interesting initial results for the benefit of the wider society. Brighton, May 2011 Dr. Clive S. Penkett vii Acknowledgments The author would like to extend his most heartfelt thanks to his supervisor, Dr.ClivePenkett.Ithasbeenagreathonourtobeabletoparticipateinthisproject under his careful guidance. His advice inboth academic and personal matters has alwaysprovenmostsoundandithasbeenapartnershipIshallcherishfortherest ofmylife.Mythanksalsogoestohislovelyfamily—Caroline,RobertandAnna, and their lovely felines Buni and Mushi. Special thanks to Prof. Philip Parsons for his continued friendship, advice and support throughout the course of my time at Sussex and with whom I shall no doubtfindmyselfcollaboratingwithfarintothefuture.Otheracademiccolleagues IliketothankareDr.IainDay,Dr.AliAbdul-SadaandDr.MartinColesfortheir expertise in NMR, Mass spectroscopy and X-ray crystallography, respectively. In addition, I thank Dr. John Turner and Dr. Eddy Viseux for their useful discussions. I have had the pleasure of supervising and working with a series of talented mastersand undergraduate students.PaulBrann, Varun Deo, Simon Cole, Rachel Kahan and Timothy Read are all thanked for their company in the laboratory, as well as their contributions to the work of the group. I have also been fortunate to share both time and office space with a diverse fellowship of people from other groups, who have all contributed towards making my Ph.D. all the more fun: Mariusz Bobin, Chris Gallop, Tara Williams, Kayla Keller, Bill Knowledon, Becky Joyce, Laura Nicholls, Rhys Williams, Brandon Kilduff, Morgan Taylor, Mat Stanley, and many members of the Parsons group. Lastly, I am forever grateful to my family. Thanks to my brothers Paul and David (and my lovely wife Emma) and my sister Laura. To my Mum and Dad, who I hope to always make proud and have never failed to support me, this is for you. ix

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Jason Woolford's thesis describes for the first time, a double [3+2] photocycloaddition of alkenes onto aromatic rings. Modern synthetic chemistry relies on the ability of researchers to uncover new and more efficient ways of creating highly complex structures. This work describes a novel, environme
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