Posts Tagged ‘immediate product’
The reaction described in the previous post (below) is an unusual example of nucleophilic attack at an sp2-carbon centre, reportedly resulting in inversion of configuration. One can break it down to a sequence of up to eight individual steps, which makes teaching it far easier. But how real is that sequence?
- T.C. Clarke, and R.G. Bergman, "Olefinic cyclization at a vinyl cation center. Inversion preference for intramolecular nucleophilic substitution by a double bond", J. Am. Chem. Soc., vol. 94, pp. 3627-3629, 1972. http://dx.doi.org/10.1021/ja00765a062
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).
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.