キハラ ノブヒロ   Kihara Nobuhiro
  木原 伸浩
   所属   神奈川大学  理学部 化学科
   職種   教授
言語種別 英語
発行・発表の年月 2003/06
形態種別 学術雑誌
査読 査読あり
標題 Dynamic Covalent Approach to [2]- and [3]Rotaxanes by Utilizing a Reversible Thiol-Disulfide Interchange Reaction
執筆形態 共著
掲載誌名 Chem. Eur. J.
巻・号・頁 9(12),pp.2895-2903
著者・共著者 Yoshio Furusho, Tomoya Oku, Toshihide Hasegawa, Akiyoshi Tsuboi, Nobuhiro Kihara, and Toshikazu Takata
概要 Sym. dumbbell-shaped compds. with two secondary ammonium centers and a central located disulfide bond were synthesized as components of rotaxanes. The rotaxanes were synthesized from the dumbbell-shaped compds. and dibenzo-[24]crown-8 (DB24C8) with catalysis by benzenethiol. The yields of isolated rotaxanes reached about 90% under optimized conditions. A kinetic study on the reaction forming [2]rotaxane 2a and [3]rotaxane 3a suggested a plausible reaction mechanism comprising several steps, including (1) initiation, (2) [2]rotaxane formation, and (3) [3]rotaxane formation. The whole reaction was found to be reversible in the presence of thiols, and thermodn. control over product distribution was thus possible by varying the temp., solvent, initial ratio of substrates, and concn. The steric bulk of the end-capping groups had almost no influence on rotaxane yields, but the structure of the thiol was crucial for reaction rates. Amines and phosphines were also effective as catalysts.
DOI 10.1002/chem.200204644
ISSN 0947-6539