Objective "The properties of organic molecules are defined by their shape andfunctionality. However, the creation of such molecules with controlover both of these features is highly challenging. This proposaldescribes novel methodology for simultaneous C-C bond formation with controlover shape (stereochemistry). In particular it focuseson the stereoselective replacement of boron (which is easy tointroduce) to halides and other heteroatoms, and new ways forcross-coupling to aromatics without the need for transition metals.In order to promote the electrophilic halogenation of a boronicester, we envisaged the reaction of boronate complex with a halogen electrophile. In preliminary experiments such processes have alreadybeen found to be viable and occur with complete stereoinversion.Through tuning the nature of the aryl lithium one could envisageselective halogenation of a broad range of substrates, giving accessto a myriad of stereodefined secondary alkyl halides, includingfluorides. Moreover, alcohols, amines derivatives, thioethers andselenoethers could all be accessible by the reaction of these newactivated boronic ester ate complexes with suitable electrophiles.The final part will focus on the (transition metal-free) crosscoupling of secondary alkylboronic esters. We present a conceptually newapproach to this challenging problem by considering the reaction of asecondary boronic ester with an aryl lithium reagent. Following atecomplex formation, one-electron oxidation would result indearomatization leading to a radical cation which would trigger a1,2-migration/rearomatization sequence. High stereointegrity can beexpected for such a process from the stereospecificity of the1,2-sigmatropic rearrangement. Preliminary results have shown thatthe concept is again viable but needs substantial optimization. This methodology will be applied tochallenges in synthesis." Fields of science natural scienceschemical sciencesinorganic chemistryalkali metalsnatural scienceschemical sciencesinorganic chemistryhalogensnatural scienceschemical sciencesorganic chemistryalcoholsnatural scienceschemical sciencesinorganic chemistrymetalloidsnatural scienceschemical sciencesorganic chemistryamines Programme(s) FP7-PEOPLE - Specific programme "People" implementing the Seventh Framework Programme of the European Community for research, technological development and demonstration activities (2007 to 2013) Topic(s) FP7-PEOPLE-2010-IEF - Marie-Curie Action: "Intra-European fellowships for career development" Call for proposal FP7-PEOPLE-2010-IEF See other projects for this call Funding Scheme MC-IEF - Intra-European Fellowships (IEF) Coordinator UNIVERSITY OF BRISTOL Address Beacon house queens road BS8 1QU Bristol GB See on map Activity type Higher or Secondary Education Establishments projects.administrative_contact Vince Boyle (Mr.) Links Contact the organisation Opens in new window Website Opens in new window EU contribution € 209 092,80
