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A Strategy toward Cyclic Topologies Based on the Dynamic Behavior of a Bis(hindered amino)disulfide Linker
Author(s) -
Tsurumi Nao,
Takashima Rikito,
Aoki Daisuke,
Kuwata Shigeki,
Otsuka Hideyuki
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201910722
Subject(s) - linker , chemistry , disulfide bond , combinatorial chemistry , sequence (biology) , transformation (genetics) , topology (electrical circuits) , radical , reactivity (psychology) , organic chemistry , computer science , gene , operating system , biochemistry , mathematics , combinatorics , medicine , alternative medicine , pathology
A simple and efficient method to generate macrocyclic structures has been developed based on the dynamic behavior of the linker bis(2,2,6,6‐tetramethylpiperidin‐1‐yl)disulfide (BiTEMPS). The prime linear structure was transformed into a (macro)cycle using the following sequence: 1) thiol–ene reaction with a BiTEMPS derivative to afford the linear precursor, then 2) an entropy‐driven transformation induced by diluting and heating. The radicals generated from BiTEMPS upon heating are highly tolerant toward a variety of chemical species, including oxygen and olefins, but they exhibit high reactivity in exchange reactions, which can be applied to the topology transformation of various skeletons. The advantages of the present method, namely, its procedural simplicity and substrate versatility, are demonstrated by the gram‐scale synthesis of cyclic compounds with low and relatively high molecular weight.