En Route to a Molecular Sheaf: Active Metal Template Synthesis of a [3]Rotaxane with Two Axles Threaded through One Ring

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• 作者：Hei Man Cheng ; David A. Leigh ; Francesca Maffei ; Paul R. McGonigal ; Alexandra M. Z. Slawin ; Jhenyi Wu
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：August 10, 2011
• 年：2011
• 卷：133
• 期：31
• 页码：12298-12303
• 全文大小：875K
• 年卷期：v.133,no.31(August 10, 2011)
• ISSN：1520-5126

文摘

We report that a 2,2鈥?6鈥?2鈥?terpyridylmacrocycle鈥揘i complex can efficiently mediate the threading of two alkyl chains with bulky end groups in an active metal template sp³-carbon-to-sp³-carbon homocoupling reaction, resulting in a rare example of a doubly threaded [3]rotaxane in up to 51% yield. The unusual architecture is confirmed by X-ray crystallography (the first time that a one-ring-two-thread [3]rotaxane has been characterized in the solid state) and is found to be stable with respect to dethreading despite the large ring size of the macrocycle. Through such active template reactions, in principle, a macrocycle should be able to assemble as many axles in its cavity as the size of the ring and the stoppers will allow. A general method for threading multiple axles through a macrocycle adds significantly to the tools available for the synthesis of different types of rotaxane architectures.