dc.contributor.authorRijs, Nicole J.
dc.contributor.authorYoshikai, Naohiko
dc.contributor.authorNakamura, Eiichi
dc.contributor.authorO’Hair, Richard A. J.
dc.date.accessioned2014-12-09T02:59:21Z
dc.date.available2014-12-09T02:59:21Z
dc.date.copyright2014en_US
dc.date.issued2014
dc.identifier.citationRijs, N. J., Yoshikai, N., Nakamura, E., & O’Hair, R. A. J. (2014). Unraveling organocuprate complexity : fundamental insights into intrinsic group transfer selectivity in alkylation reactions. The journal of organic chemistry, 79(3), 1320-1334.en_US
dc.identifier.urihttp://hdl.handle.net/10220/24362
dc.description.abstractThe near thermal conditions of an ion-trap mass spectrometer were used to examine the intrinsic gas-phase reactivity and selectivity of nucleophilic substitution reactions. The well-defined organocuprate anions [CH3CuR]– (R = CH3CH2, CH3CH2CH2, (CH3)2CH, PhCH2CH2, PhCH2, Ph, C3H5, and H) were reacted with CH3I. The rates (reaction efficiencies, ϕ) and selectivities (the product ion branching ratios) were compared with those of [CH3CuCH3]– reacting with CH3I. Alkyl R groups yielded similar efficiencies, with selectivity for C–C bond formation at the coordinated R group. Inclusion of unsaturated R groups curbed the overall reactivity (ϕ = 1 to 2 orders of magnitude lower). With the exception of R = PhCH2CH2, these switched their selectivity to C–C bond formation at the CH3 group. Replacing an organyl ligand with R = H significantly enhanced the reactivity (8-fold), resulting in the selective formation of methane. Unique decomposition and side-reactions observed include: (1) spontaneous β-hydride elimination from [RCuI]– byproducts; and (2) homocoupling of the pre-existing organocuprate ligands in [CH3CuC3H5]–, as shown by deuterium labeling. DFT (B3LYP-D/Def2-QZVP//B3LYP/SDD:6-31+G(d)) predicts that the alkylation mechanism for all species is via oxidative addition/reductive elimination (OA/RE). OA is the rate-limiting step, while RE determines selectivity: the effects of R on each were examined.en_US
dc.format.extent42 p.en_US
dc.language.isoenen_US
dc.relation.ispartofseriesThe journal of organic chemistryen_US
dc.rights© 2014 American Chemical Society. This is the author created version of a work that has been peer reviewed and accepted for publication by The Journal of Organic Chemistry, American Chemical Society. It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [Article DOI: http://dx.doi.org/10.1021/jo4027325].en_US
dc.subjectDRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds
dc.titleUnraveling organocuprate complexity : fundamental insights into intrinsic group transfer selectivity in alkylation reactionsen_US
dc.typeJournal Article
dc.contributor.schoolSchool of Physical and Mathematical Sciencesen_US
dc.identifier.doihttp://dx.doi.org/10.1021/jo4027325
dc.description.versionAccepted versionen_US


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