Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Studies on Hydrogenolysis. LIV. Catalytic Hydrogenolysis of Optically Active 2-Methyl-2-phenylaziridine
Yoshihiro SugiSekio Mitsui
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1969 Volume 42 Issue 10 Pages 2984-2989

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Abstract

In order to obtain further information about the catalytic hydrogenolysis of benzyl-type compounds, the hydrogenolysis of optically active 2-methyl-2-phenylaziridine (I) over several group VIII transition metal catalysts was investigated in ethanol under ordinary pressure and at room temperature. 2-Phenylpropylamine (II) was obtained as the main product over all the catalysts. The configuration of II was inverted over the palladium catalyst. However, the hydrogenolysis over the platinum catalyst occurred with a significant retention of the configuration. Further, in the case of Raney nickel and Raney cobalt catalysts, the configurations of II were retained with the low stereoselectivities, and a small amount of 2-phenyl-2-propylamine (III) was also produced in addition to II. These results are attributable to the free-energy difference at the transition states to form π-benzyl intermediates, which depends on the affinity of these metals for the nitrogen lone-pair, the catalyst hindrance, and other factors. The SN2-type reaction is favored over the palladium catalyst. On the other hand, the SNi-type reaction is favored over platinum, Raney nickel, and Raney cobalt catalysts, where the radical-cleavage reaction will participate in addition to the SNi-type reaction over the latter two catalysts. The differences in behavior between styrene imines and styrene oxides on the catalyst surface were also discussed.

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