Stereoselective Synthesis of 5-7 membered Cyclic Ethers by Deiodonative Ring-Enlargement Using Hypervalent Iodine Reagents 英文参考文献.docVIP

Molecules 2005, 10, 183-189 molecules ISSN 1420-3049 Stereoselective Synthesis of 5-7 membered Cyclic Ethers by Deiodonative Ring-Enlargement Using Hypervalent Iodine Reagents Tomohito Abo, Masanori Sawaguchi, Hisanori Senboku and Shoji Hara* Division of Molecular Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan. Tel. +81-11-706-6556, Fax +81-11-706-6556. *Author to whom correspondence should be addressed, e-mail:hara@org-mc.eng.hokudai.ac.jp Received: 19 April 2004 / Accepted: 15 July 2004 / Published: 31 January 2005 Abstract: Stereoselective synthesis of 5-7 membered cyclic ethers was achieved by deiodonative ring-enlargement of cyclic ethers having an iodoalkyl substituent. The reaction took place readily under mild conditions using hypervalent iodine compounds and an acetoxy or a trifluoroacetoxy group was introduced into the rings depending on the hypervalent iodine reagent employed. The use of hexafluoroisopropanol (HFIP) as solvent is critical. Keywords: Ring-enlargement, cyclic ether, hypervalent iodine compounds. Introduction Recently, we found that 5-7 membered fluoro cyclic ethers 2 can be stereoselectively prepared from 4-6 membered ones having an iodoalkyl substituent at the 2-position, 1, by the fluorinative ring-enlargement reaction induced by iodotoluene difluoride [1]. During our continued study of ring-enlargement reaction of cyclic ethers 1 using hypervalent iodine compounds, we found that cyclic ether having an acetoxy or a trifluoroacetoxy group, key intermediates for the synthesis of cyclic polyether natural compounds [2-5], can be stereoselectively synthesized by the reaction with (diacetoxyiodo)toluene (DIT) or [bis(trifluoroacetoxy)]iodobenzene (BTI).  Molecules 2005, 10 184 R1 R1 O R2 ArIX2 O R2 (1) I (CH2)n R3 (CH2)n 1 X R3 2 : X = F 3 : X = OAc 4 : X = OCOCF 3 Results and Discussion