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Vinylcyclopropane-cyclopentene Rearrangement
The vinylcyclopropane rearrangement or vinylcyclopropane-cyclopentene rearrangement is a ring expansion reaction, converting a vinyl-substituted cyclopropane ring into a cyclopentene ring. Intense experimental as well as computational investigations have revealed that mechanistically, the vinylcyclopropane rearrangement can be thought of as either a diradical-mediated two-step and/or orbital-symmetry-controlled pericyclic process. The amount by which each of the two mechanisms is operative is highly dependent on the substrate. Due to its ability to form cyclopentene rings the vinylcyclopropane rearrangement has served several times as a key reaction in complex natural product synthesis. Origins and history In 1959, a young research chemist with Humble Oil and Refining (Esso, now Exxon) named Norman P. Neureiter was instructed to find new uses for the excess butadiene produced from one of the refinery processes. Discussions about carbene chemistry with one of the company's most ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Ring Expansion Reaction
Ring expansion and ring contraction reactions in the course of organic synthesis refer to a set of reactions which can lead to the expansion or contraction of an existing Ring (chemistry), ring. This often makes it possible to access structures that would be difficult if not impossible to synthesise with single cyclization reactions. Ring expansions are valuable because they allow access to larger systems that are difficult to synthesize through a single cyclization due to the slow rate of formation. Ring contractions are useful for making smaller, more strained rings from larger rings. Expansions are classified by the mechanism of expansion and the atom(s) added; contractions are characterized simply by the reactive intermediate which performs the contraction. Description In the course of an organic synthesis, a chemist often needs to form a new or alter an existing ring. Ring expansion and ring contraction reactions are used to expand or contract an existing Ring (chemistry) ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
