Ring-Expansion Reaction of Oximes with Aluminum Reductants 英文参考文献.docVIP

Molecules 2012, 17, 7348-7355; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Ring-Expansion Reaction of Oximes with Aluminum Reductants Hidetsura Cho 1,2,*, Yusuke Iwama 2, Nakako Mitsuhashi 2, Kenji Sugimoto 2, Kentaro Okano 2 and Hidetoshi Tokuyama 2,* 1 Graduate School of Science, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai 980-8578, Japan 2 Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai 980-8578, Japan * Authors to whom correspondence should be addressed; E-Mails: hcho@mail.pharm.tohoku.ac.jp (H.C.); tokuyama@mail.pharm.tohoku.ac.jp (H.T.); Tel.: +81-22-795-6887 (H.T.); Fax: +81-22-795-6877 (H.T.). Received: 5 April 2012; in revised form: 4 June 2012 / Accepted: 7 June 2012 / Published: 14 June 2012 Abstract: The ring-expansion reactions of heterocyclic ketoximes and carbocyclic ketoximes with several reductants such as AlHCl2, AlH3 (alane), LiAlH4, LiAlH(OtBu)3, and (MeOCH2CH2O)2AlH2Na (Red-Al) were examined. Among reductants, AlHCl2 (LiAlH4:AlCl3 = 1:3) in cyclopentyl methyl ether (CPME) has been found to be a suitable reagent for the reaction, and the rearranged cyclic secondary amines were obtained in good to excellent yields. Keywords: aluminum reductant; dichloroaluminum hydride (AlHCl2); ring-expansion of oxime; rearrangement of oxime; cyclopentyl methyl ether (CPME) 1. Introduction The development of novel synthetic method of constructing basic heterocyclic skeletons is an important research topic from the viewpoint of both synthetic chemistry and medicinal chemistry. Specifically, the fundamental skeletons containing a nitrogen functionality attached to an aromatic ring are of great importance because they are often used as the core structures of medicines or clinical candidates. In this research area, we have recently reported the synthesis of five- to eight-membe