40648-08-6Relevant articles and documents
Selectivity in the Reactions of Less Stable Carbocations with Magnesium Halides in Aprotic Solvents. A Theoretical Approach to the Constant Selectivity Principle.
Martinez, A. Garcia,Alvarez, R. Martinez,Vilar E. Teso,Fraile, A. Garcia,Barcina, J. Osio,Subramanian, L. R.
, p. 7077 - 7084 (2007/10/02)
The solvolysis of 7,7-bis(trifluoromethylsulfonyloxy)-2-norbornene (1a), 1-trifluoromethylsulfonyloxy-1-phenylethylene (2a), 2-methyl-1-cyclohexen-1-yl triflate (3a) and 4-camphenyl triflate (4a) in carbon disulfide or diethyl ether with added MgI2 and MgBr2 yields a mixture of the corresponding halides 5b-e, 6b-c, 7b-c and 8b-c.The ionization of the triflate group is favoured by coordination with the magnesium halide.The reaction with MgI2 was found to be second-order and is about 50 times more reactive than MgBr2.The selectivities of the intermediate cations 5-8 toward the nucleophiles MgI2 and MgBr2 are nearly constant, although the solvolysis rates differ by more than three powers of ten.A theoretical explanation of the constant selectivity principle is given.
Novel Bicyclization Methodology via Cyclialkylation of ω-Halo-1-metallo-1-alkynes Containing Aluminium and Zinc
Negishi, Ei-ichi,Sawada, Hiroyuki,Tour, James M.,Wei, Yuanyang
, p. 913 - 915 (2007/10/02)
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