2014-Angew-硅亲核.pdf

. Angewandte Communications DOI: 10.1002/anie.201403726 Small Ring Systems Silylative Cyclopropanation of Allyl Phosphates with Silylboronates** Ryo Shintani,* Ryuhei Fujie, Momotaro Takeda, and Kyoko Nozaki* Abstract: A potassium-bis(trimethylsilyl)amide-mediated intermediates have been reported by using enolate-based cyclopropanation of allyl phosphates with silylboronates has carbon nucleophiles for intermolecular reactions, as well as been developed. Unlike the reported copper-catalyzed allylic nitrogen[5] and oxygen[6] nucleophiles for intramolecular substitution reactions, the nucleophile selectively attacks at the cyclization reactions, but the use of other heteroatom b-position of the allylic substrates under the present reaction nucleophiles has been scarcely explored. In fact, a copper- conditions. The mechanism of this process has also been catalyzed intermolecular borylative cyclopropanation[7] and investigated, thus indicating the involvement of a silylpotassium an intramolecular silylative cyclopropanation using elaborate species as the active nucleophilic component. (allyloxy)silyllithiums generated in situ[8] have only been reported as far as we are aware. In this context, we herein Changing the existing reaction patterns to unusual ones by describe the development of a potassium-bis(trimethylsilyl)-