AI Article Synopsis
- Carefully controlling reaction temperature allows tBuLi treatment of aryl benzyl ethers to lead to selective α-lithiation, creating stable organolithiums.
- These organolithiums can be trapped with various electrophiles before going through a [1,2]-Wittig rearrangement.
- The study shows that aryl α-lithiated benzyl ethers with electron-poor aryl groups favor an anionic rearrangement pathway due to their stability and preferential behavior.
Article Abstract
By carefully controlling the reaction temperature, treatment of aryl benzyl ethers with tBuLi selectively leads to α-lithiation, generating stable organolithiums that can be directly trapped with a variety of selected electrophiles, before they can undergo the expected [1,2]-Wittig rearrangement. This rearrangement has been deeply studied, both experimentally and computationally, with aryl α-lithiated benzyl ethers bearing different substituents at the aryl ring. The obtained results support the competence of a concerted anionic intramolecular addition/elimination sequence and a radical dissociation/recombination sequence for explaining the tendency of migration for aryl groups. The more favored rearrangements are found for substrates with electron-poor aryl groups that favor the anionic pathway.
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| http://dx.doi.org/10.1002/chem.201602254 | DOI Listing |
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