Divergent and selective rearrangements of vinylcyclopropanes into 1,4-dienes and cyclopentenes
(2019)
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- Authors
- Supervisors
- Robiette, Raphael
- Abstract
- The formation of five-membered carbocycles is a fundamental and important issue in organic synthesis, this scaffold being part of a large amount of biologically active compounds. Cycloaddition or annulation strategies have been described but these reactions requires very specific reactants and thereby are restrictive. Accordingly, we propose to develop a general and effective (3+2) annulation strategy toward five-membered carbocycles by investigating the reaction between activated olefins and sulfonium ylides. This strategy proceed via a (2+1) annulation leading to a vinylcyclopropane intermediate that is further rearranged into a cyclopentene under a Lewis acid catalysis. In the course of our studies to establish the optimal reaction conditions for this rearrangement, we discovered the possibility to access 1,4-dienes (also called skipped dienes) from the same vinylcyclopropane intermediate. Therefore, owing the ubiquity of 1,4-dienes in organic chemistry and the challenge that represents their synthesis, we decided to develop a divergent methodology leading selectively either to cyclopentenes or 1,4-dienes from a common vinylcyclopropane intermediate. Presently, this strategy constitute a novel interesting method to synthesize cyclopentenes and especially 1,4-dienes. Indeed, this work provide an efficient tool to access C3 substituted 1,4-dienes from readily available reactants with a great efficiency and atom economy. We also build a theoretical model describing in details the rearrangement of the vinylcyclopropane into the targeted structures.
- Affiliations
Citations
Richald, M. (2019). Divergent and selective rearrangements of vinylcyclopropanes into 1,4-dienes and cyclopentenes. https://hdl.handle.net/2078.5/124657