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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
One-pot synthesis of a [c2]daisy-chain-containing hetero[4]rotaxane via a self-sorting strategy
Xin Fu1, Qi Zhang1, Si-Jia Rao1
1Key Laboratory for Advanced Materials and Institute of Fine Chemicals , East China University of Science and Technology , 130 Meilong Road , Shanghai , 200237 , China .
Abstract:
The construction and efficient synthesis of hetero[n]rotaxanes with high structural complexity are always attractive challenges. Herein, we demonstrate a facile one-pot preparation of a hetero[4]rotaxane, by employing a self-sorting strategy, which contains an interpenetrated dibenzo-24-crown-8 (DB24C8) based [c2]daisy chain structure and is ended with a benzo-21-crown-7 (B21C7) based rotaxane at each side. The key to the design involved encoding the selective threading using a steric hindrance-related "language", where highly selective self-assemblies occurred in a three-component self-sorting process, which included the threading of a benzylalkylammonium into a B21C7 and interpenetrated dimerized formation of a DB24C8 based [c2]daisy chain simultaneously; the precise pre-assembled system resulted in the efficient synthesis of hetero[4]rotaxane with a high-level of structural complexity under the "CuAAC" reaction.
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Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.