Posts Tagged ‘Baldwins rules’

Transition state models for Baldwin dig(onal) ring closures.

Sunday, June 10th, 2012
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This is a continuation of the previous post exploring the transition state geometries of various types of ring closure as predicted by  Baldwin’s rules. I had dealt with bond formation to a trigonal (sp2) carbon; now I add a digonal (sp) example (see an interesting literature variation). 

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Transition state models for Baldwin’s rules of ring closure.

Saturday, June 2nd, 2012
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The Baldwin rules for ring closure follow the earlier ones by Bürgi and Dunitz in stating the preferred angles of nucleophilic (and electrophilic) attack in bond forming reactions, and are as famous for the interest in their exceptions as for their adherence. Both sets of rules fundamentally explore the geometry of the transition states involved in the reaction, as reflected in the activation free energies. Previous posts exploring the transition states for well-known reactions have revealed that the 4th dimension (the timing of the bond formations/breakings) can often spring surprises. So this post will explore a typical Baldwin ring formation in the same way.

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