The Double [3+2] Photocycloaddition Reaction

199 Pages·2011·1.71 MB·English

by  Jason A. Woolford (auth.)

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Jason A. Woolford
The Double [3+2]
Photocycloaddition
Reaction
Doctoral Thesis accepted by
University of Sussex, UK
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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
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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
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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
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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.
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