Journal of Organic Chemistry 2010-11-05

Efforts toward distorted spiropentanes.

Kuan-Jen Su, Jean-Luc Mieusset, Vladimir B Arion, Wolfgang Knoll, Lothar Brecker, Udo H Brinker

Index: J. Org. Chem. 21th ed., 75 , 7494-7497, (2010)

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Abstract

Tetravinylbenzene 4 was prepared in nearly quantitative yield from commercially available tetrabromobenzene; the improved, one-step procedure now employs Suzuki-Miyaura cross-coupling conditions. Intermolecular cyclopropanation of 4 with dibromocarbene gave a series of gem-dibromide adducts. Intramolecular cyclopropanation of monoadduct 5, putatively by its methyllithium-generated cyclopropylidene(oid), produced compound 11, which features a highly distorted spiropentane having a C-C-C bond angle of 163.5°. The stability of the reported spiropentanes was investigated using DFT calculations.


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