通过串联1,3-偶极环加成/消除反应，经由螺环吡唑啉中间体合成1,3,5-三取代吡唑的新方法。
A Novel Synthesis of 1,3,5-Trisubstituted Pyrazoles through a Spiro-pyrazoline Intermediate via a Tandem 1,3-Dipolar Cycloaddition/Elimination.
作者信息
Dadiboyena Sureshbabu, Valente Edward J, Hamme Ashton T
机构信息
Department of Chemistry, College of Science, Engineering and Technology, Jackson State University, Jackson, Mississippi 39217 USA.
出版信息
Tetrahedron Lett. 2009 Jan 21;50(3):291. doi: 10.1016/j.tetlet.2008.10.145.
Abstract
The syntheses of an important class of hitherto unreported 1,3,5-pyrazoles, inspired by an unanticipated eliminatory ring opening are described. The reported pyrazole compounds were constructed through the Huisgen cyclization of 2-methylene-1,3,3-trimethylindoline and an in situ generated nitrile imine. The newly formed spiro-pyrazoline intermediate presumably then undergoes a ring opening/elimination process to afford a pyrazole, as evidenced by single X-ray crystal data. The current report constitutes the first formal observation of this kind of ring opening involving a spiro-pyrazoline intermediate.
摘要
本文描述了一类迄今为止尚未报道的1,3,5-吡唑的合成，该合成受到意外的消除开环反应的启发。所报道的吡唑化合物是通过2-亚甲基-1,3,3-三甲基吲哚啉与原位生成的腈亚胺的惠斯根环化反应构建而成。新形成的螺吡唑啉中间体可能随后经历开环/消除过程以得到吡唑，单晶X射线晶体数据证明了这一点。本报告首次正式观察到这种涉及螺吡唑啉中间体的开环反应。
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1
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Org Lett. 2008 Mar 20;10(6):1307-10. doi: 10.1021/ol800200j. Epub 2008 Feb 27.
2
Reaction of N-monosubstituted hydrazones with nitroolefins: a novel regioselective pyrazole synthesis.N-单取代腙与硝基烯烃的反应：一种新型区域选择性吡唑合成方法。
Org Lett. 2006 Aug 3;8(16):3505-8. doi: 10.1021/ol061226v.
3
An entry to a chiral dihydropyrazole scaffold: enantioselective [3 + 2] cycloaddition of nitrile imines.手性二氢吡唑骨架的构建：腈亚胺的对映选择性[3 + 2]环加成反应
J Am Chem Soc. 2005 Jun 15;127(23):8276-7. doi: 10.1021/ja051650b.
4
Regioselective synthesis of polysubstituted pyrazoles and isoxazoles.
J Org Chem. 2001 Oct 5;66(20):6787-91. doi: 10.1021/jo0101407.
5
Versatile and efficient solid-phase syntheses of pyrazoles and isoxazoles.
Org Lett. 2000 Sep 7;2(18):2789-92. doi: 10.1021/ol006197h.
6
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J Med Chem. 1997 Apr 25;40(9):1347-65. doi: 10.1021/jm960803q.
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