Journal article
Gas-phase reactivity of group 11 dimethylmetallates with allyl iodide
NJ Rijs, N Yoshikai, E Nakamura, RAJ O'Hair
Journal of the American Chemical Society | Published : 2012
DOI: 10.1021/ja2069032
Abstract
Copper-mediated allylic substitution reactions are widely used in organic synthesis, whereas the analogous reactions for silver and gold are essentially unknown. To unravel why this is the case, the gas-phase reactions of allyl iodide with the coinage metal dimethylmetallates, [CH 3MCH 3] - (M = Cu, Ag and Au), were examined under the near thermal conditions of an ion trap mass spectrometer and via electronic structure calculations. [CH 3CuCH 3] - reacted with allyl iodide with a reaction efficiency of 6.6% of the collision rate to yield: I - (75%); the cross-coupling product, [CH 3CuI] - (24%); and the homo-coupling product, [C 3H 5CuI] - (1%). [CH 3AgCH 3] - and [CH 3AuCH 3] - reacted subs..
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Awarded by Japan Society for the Promotion of Science
Funding Acknowledgements
We thank the ARC for financial support via grant DP110103844 (to R.A.J.O.) and through the ARC CoE program. N.J.R. 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; and (iii) the Global COE Program for Chemistry Innovation (MEXT, Japan) for partial support of the research in Tokyo. The Victorian Partnership for Advanced Computing (VPAC) and the Chemical Sciences High Performance Computing Facility (Gomberg) are acknowledged for generous provision of computational resources.