Journal article
Unraveling organocuprate complexity: Fundamental insights into intrinsic group transfer selectivity in alkylation reactions
NJ Rijs, N Yoshikai, E Nakamura, RAJ O'Hair
Journal of Organic Chemistry | Published : 2014
DOI: 10.1021/jo4027325
Abstract
The 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 [CH 3CuR]- (R = CH3CH2, CH 3CH2CH2, (CH3)2CH, PhCH2CH2, PhCH2, Ph, C3H 5, and H) were reacted with CH3I. The rates (reaction efficiencies,) 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 (= 1 to 2 orders of magnitude lower). With the exception of..
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Awarded by Australian Research Council
Funding Acknowledgements
We thank the ARC for financial support via grant DP110103844 (to RAJO) and through the ARC CoE program. NJR thanks: (i) The University of Melbourne Faculty of Science for a Science Faculty Scholarship; (ii) The University of Melbourne for a Postgraduate Overseas Research Experience Scholarship (PORES) to travel to the University of Tokyo; (iii) the Specially Promoted Research Grant from MEXT, Japan (KAKENHI 22000008 to E.N.); and (iv) support from the AvH foundation. The Victorian Partnership for Advanced Computing (VPAC) and the Chemical Sciences High Performance Computing Facility (Gomberg) are acknowledged for generous provision of computational resources.