Henry Rzepa's Blog Chemistry with a twist

November 30, 2012

A pericyclic dichotomy.

Filed under: Uncategorised — Tags: , , , , , — Henry Rzepa @ 9:09 am

A dichotomy is a division into two mutually exclusive, opposed, or contradictory groups. Consider the reaction below. The bicyclic pentadiene on the left could in principle open on heating to give the monocyclic [12]-annulene (blue or red) via what is called an electrocyclic reaction as either a six (red) or eight (blue) electron process. These two possibilities represent our dichotomy; according to the Woodward-Hoffmann (WH) pericyclic selection rules, they represent contradictory groups. Depending on the (relative) stereochemistry at the ring junctions, if one reaction is allowed by the WH rules, the other must be forbidden, and of course vice-versa. It is a nice challenge to ask students to see if the dichotomy can be reconciled.


July 10, 2011

The stereochemistry of [8+2] pericyclic cycloadditions.

Steve Bachrach has blogged on the reaction shown below. If it were a pericyclic cycloaddition, both new bonds would form simultaneously, as shown with the indicated arrow pushing. Ten electrons would be involved, and in theory, the transition state would have 4n+2 aromaticity. In fact Fernandez, Sierra and Torres have reported that they can trap an intermediate zwitterion 2, and in this sense therefore, the reaction is not pericyclic but nucleophilic addition from the imine lone pair to the carbonyl of the ketene (it finds the half way stage convivial). But this got me thinking. Does this reaction have any pericyclic character at all? And if so, could it be enhanced by design?


February 13, 2011

Valentine chemistry

Filed under: General — Tags: , , , , , , — Henry Rzepa @ 11:53 am

The Möbius band is an experimental delight. In its original forms, it came flat-packed as below. The one shown on the left is related to the international symbol for recycling (if we denote the number of half twists imparted as m, this one has m=3). The middle one (m=4) shows a 4-twisted variant, and the one on the right has a 5-twist (m=5). These all come from Möbius’ original sketches, found amongst his belongings when he died. In this post they will form the basis for some experiments in molecular chirality.


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