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- W1483603599 abstract "The hydrogenation and isomerization of alkenes can usually be described by the classical Horiuti–Polfinyi mechanism. According to that mechanism, in a deuterium atmosphere, double bond migration incorporates deuterium into the allylic position. Early experiments using (+)-apopinene and deuterium showed, however, that in the isomerized molecules the deuterium content was very low and the isomerization was much faster than deuterium incorporation into the allylic position. Therefore, it seemed probable that isomerization takes place through an intramolecular hydrogen shift. A sigmatropic 1, 3-hydrogen shift was suggested, in which the allylic endo-H shifted (top shift). Although this type of reaction is symmetry forbidden in an unadsorbed molecule, theoretical calculations showed that in a molecule adsorbed on transition metals, such a shift is allowed. Later, other theoretical calculations suggested another type of 1, 3-hydrogen shift, one in which the allylic exo-hydrogen is abstracted by the surface from an adsorbed alkene (either 1, 2-diadsorbed or π-complexed) and the resulting π-allyl species move over the abstracted hydrogen in such a way that it adds to the former vinylic position and causes, in effect, a stepwise intramolecular 1,3-hydrogen shift (bottom shift). To distinguish between these two hydrogen shift mechanisms, (1S)-(-)-exo-2, 4-dideuteroapopinene was constructed as a probe molecule. A top shift of the allylic endo-H will not affect the deuterium content of the molecule and no change should occur in the hydrogen content at any position, but a bottom shift of the allylic exo-D will decrease deuterium in the vinylic position (C2) and increase deuterium in the allylic position (C4)." @default.
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- W1483603599 date "1996-01-01" @default.
- W1483603599 modified "2023-09-25" @default.
- W1483603599 title "Racemization of (1S)-(−)-exo-2,4-dideuteroapopinene over Pd: Evidence for an Intramolecular 1,3-deuterium shift" @default.
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- W1483603599 doi "https://doi.org/10.1016/s0167-2991(96)80235-7" @default.
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