Efforts toward Distorted Spiropentanes

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.