The double [3+2] photocycloaddition reaction

Woolford, Jason A. (2010) The double [3+2] photocycloaddition reaction. Doctoral thesis (DPhil), University of Sussex.

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One of a synthetic organic chemists‟ greatest challenges is to create step-efficient routes toward compounds with high molecular complexity. Therefore, reactions such as the meta
photocycloaddition of an olefin to a benzene derivative, which provide more than one bond in a single step are of significant importance. It this remarkable reaction three new σ bonds, three new rings and up to six new stereocenters are formed simultaneously. Additional complexity can be added by tethering the two reacting partners together and this form of the reaction has found many uses in natural product synthesis.

In this work a remarkable double [3+2] photocycloaddition reaction is reported that results in the formation of a complex cis, cis, cis, trans-[5, 5, 5, 5] fenestrane derivative from a simple flat aromatic acetal with two branching alkenes. During this dramatic transformation four carboncarbon bonds, five new rings and seven new stereocenters are created in a single one-pot process using only UV light. The reaction occurs in a sequential manner from the linear meta photocycloadduct, via a secondary [3+2] addition of the alkene across the cyclopropane of the adduct. In addition, an angular meta photocycloadduct also produced in the initial addition step, undergoes an alternative fragmentation-translocation photoreaction to afford a silphinene-like angular tricyclic compound.

In this work the investigation of this newly discovered process is discussed via the synthesis and subsequent irradiation of a series of photosubstrates containing different functional groups in the arene-alkene tether. In addition, attempts toward the synthesis of alternative structures using the same double [3+2] photocycloaddition are reported.

Item Type: Thesis (Doctoral)
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry
Depositing User: Library Cataloguing
Date Deposited: 25 Jan 2011 13:10
Last Modified: 13 Aug 2015 15:09
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