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Topic: Photochemical [1,3] sigmatropic rearrangement  (Read 1445 times)

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Offline CrazyAssasin

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Photochemical [1,3] sigmatropic rearrangement
« on: August 22, 2014, 04:54:52 PM »
According to Woodward-Hoffmann rules photochemical [1,3] shift is allowed suprafacially and theoretically this reaction is possible to happen just as [1,5] shift does thermally. But for some reason there are no such kind of migration of double bonds across a molecule, and if it was possible I believe for example double bonds of unsaturated fatty acid should become conjugated with carbonyl under intensive exposure to light. So why don't we see any effect of [1,3] shift?

Offline Irlanur

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Re: Photochemical [1,3] sigmatropic rearrangement
« Reply #1 on: August 25, 2014, 05:34:47 PM »
you could argue with FMO-theory (or orbital correlation diagrams or state correlation diagrams...)

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