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dc.contributor.authorTaylor, Laurence J.
dc.contributor.authorBuehl, Michael
dc.contributor.authorChalmers, Brian A.
dc.contributor.authorRay, Matthew J.
dc.contributor.authorWawrzyniak, Piotr
dc.contributor.authorWalton, John C.
dc.contributor.authorCordes, David B.
dc.contributor.authorSlawin, Alexandra M. Z.
dc.contributor.authorWoollins, J. Derek
dc.contributor.authorKilian, Petr
dc.identifier.citationTaylor , L J , Buehl , M , Chalmers , B A , Ray , M J , Wawrzyniak , P , Walton , J C , Cordes , D B , Slawin , A M Z , Woollins , J D & Kilian , P 2017 , ' Dealkanative main group couplings across the peri-gap ' , Journal of the American Chemical Society , vol. 139 , no. 51 , pp. 18545-18551 .
dc.identifier.otherPURE: 251693563
dc.identifier.otherPURE UUID: 77ad715b-fd42-4840-9d33-22933baffc0d
dc.identifier.otherScopus: 85038570545
dc.identifier.otherORCID: /0000-0002-1095-7143/work/48131749
dc.identifier.otherORCID: /0000-0002-5366-9168/work/39487833
dc.identifier.otherORCID: /0000-0002-2999-2272/work/55901228
dc.identifier.otherORCID: /0000-0003-2746-6276/work/56638710
dc.identifier.otherORCID: /0000-0002-9527-6418/work/56861557
dc.identifier.otherORCID: /0000-0001-6379-3026/work/58285399
dc.identifier.otherORCID: /0000-0002-1498-9652/work/59464673
dc.identifier.otherWOS: 000419082100026
dc.descriptionThis work was financially supported by the EPSRC and COST action CM1302 SIPs.en
dc.description.abstractHere, we highlight the ability of peri-substitution chemistry to promote a series of unique P–P/P–As coupling reactions, which proceed with concomitant C–H bond formation. This dealkanative reactivity represents an interesting and unexpected expansion to the established family of main-group dehydrocoupling reactions. These transformations are exceptionally clean, proceeding essentially quantitatively at relatively low temperatures (70–140 °C), with 100% diastereoselectivity in the products. The reaction appears to be radical in nature, with the addition of small quantities of a radical initiator (azobisisobutyronitrile) increasing the rate dramatically, as well as altering the apparent order of reaction. DFT calculations suggest that the reaction involves dissociation of a phosphorus centred radical (stabilised by the peri-backbone) to the P–P coupled product and a free propyl radical, which carries the chain. This unusual reaction demonstrates the powerful effect that geometric constraints, in this case a rigid scaffold, can have on the reactivity of main group species; an area of research that is gaining increasing prominence in recent years.
dc.relation.ispartofJournal of the American Chemical Societyen
dc.rightsCopyright © 2017 American Chemical Society. This work has been made available online in accordance with the publisher’s policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at:
dc.subjectQD Chemistryen
dc.titleDealkanative main group couplings across the peri-gapen
dc.typeJournal articleen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.contributor.institutionUniversity of St Andrews. Office of the Principalen
dc.description.statusPeer revieweden

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