Rearrangements of organometallic compounds : X. The mechanism of 1,2-aryl migration in the Wittig rearrangement of α-metallated benzyl aryl ethers |
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| Authors: | John J Eisch Csaba A Kovacs Sue-Goo Rhee |
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| Institution: | Departments of Chemistry, The Catholic University of America, Washington, D.C. 20017 U.S.A.;The State University of New York at Binghamton, Binghamton, New York 13901 U.S.A. |
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| Abstract: | The mechanism of 1,2-aryl shifts in the Wittig rearrangement of α-metallated benzyl aryl ethers has been investigated by a detailed examination of the behavior of the following ethers: benzyl phenyl ether, benzyl para-tert-butyl- and meta-tert-butyl-phenyl ethers, benzyl 2-bromo-4-tert-butylphenyl ether and dibenzob,d] pyran. The failure to trap any aldehyde intermediate, the ease of rearrangement for the pyran, the lack of evidence for an aryne intermediate with the benzyl butyl ethers and other circumstantial evidence have led to the proposal of an intramolecular pathway in which radical pairs are generated and then collapse to the isomeric carbinolate. |
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| Keywords: | Inquiries may be directed to this author at Binghamton |
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