[5]Radialene
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- 作者：Emily G. Mackay ; Christopher G. Newton ; Henry Toombs-Ruane ; Erik Jan Lindeboom ; Thomas Fallon ; Anthony C. Willis ; Michael N. Paddon-Row ; Michael S. Sherburn
- 刊名：Journal of the American Chemical Society
- 出版年：2015
- 出版时间：November 25, 2015
- 年：2015
- 卷：137
- 期：46
- 页码：14653-14659
- 全文大小：545K
- ISSN：1520-5126
文摘
The [n]radialenes are a unique family of fundamental [n]-membered carbocyclic structures with radiating alkenes, which have attracted significant synthetic and theoretical attention. Whereas [3]-, [4]-, and [6]radialenes have been prepared and studied, all efforts to synthesize the five-membered ring compound have thus far met with failure. Here we describe the first synthesis of the fundamental hydrocarbon [5]radialene, C10H10. Our approach was a departure from previous radialene syntheses in that it utilized a low-temperature decomplexation of a stable organometallic compound, rather than high-temperature elimination or rearrangement. Our strategy was guided by analysis of previous radialene syntheses, which indicated rapid decomposition in oxygen, and ab initio calculations, which revealed an extraordinary susceptibility of [5]radialene to undergo Diels鈥揂lder dimerization/polymerization. The origin of this susceptibility was traced to a small distortion energy associated with the formation of the transition structure geometry from the relaxed reactant monomers and to a narrow HOMO鈥揕UMO gap.