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ChemInform Abstract: Novel [1,N]-Carbon to Carbon Rearrangement of an Ester Group via Organotitanium Intermediates Wherein the N Varies from 2 to 5. Full Scope and Limitation Leading Predominantly to the Rearrangement.

✍ Scribed by T. YAMAZAKI; H. URABE; F. SATO


Publisher
John Wiley and Sons
Year
2010
Weight
43 KB
Volume
29
Category
Article
ISSN
0931-7597

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✦ Synopsis


Novel [1,N]-Carbon to Carbon Rearrangement of an Ester Group via Organotitanium Intermediates Wherein the N Varies from 2 to 5. Full Scope and Limitation Leading Predominantly to the Rearrangement.

-Olefinic or acetylenic di-or tricarboxylates are shown to undergo a novel type of carbon-to-carbon rearrangement of the ethoxycarbonyl groups mediated by a (η 2 -propene)Ti(O-iPr) 2 complex. Thus, the vinylmalonate (I) undergoes a 1,2-rearrangement, while for 1,3-, 1,4-, or 1,5-rearrangements the presence of an acetylene side chain is required. In the latter case, the rearrangements afford the corresponding olefins in E-geometry. Dealkynylation is observed to be a side process. -(YAMAZAKI, T.;