C2-C6 热 [2 + 2]环化反应：烯炔-allenes 的可逆自由基形成。
The thermal C2-C6/[2 + 2] cyclisation of enyne-allenes: reversible diradical formation.
机构信息
Department of Chemistry and Biology, Universität Siegen, Siegen, Germany.
出版信息
Org Biomol Chem. 2011 May 21;9(10):3776-9. doi: 10.1039/c0ob01275k. Epub 2011 Apr 12.
PMID:21483984
Abstract
New enyne-allenes, structurally designed toward the thermal C(2)-C(6)/[2 + 2] cyclisation mode, were prepared and characterised, one of them even by X-ray crystallography. The mechanism of their transformation to formal [2 + 2] cycloadducts was interrogated by trapping experiments and DFT computations. The results support a stepwise mechanism that involves the reversible formation of the C(2)-C(6) diradical intermediate.
摘要
新型烯炔-烯丙炔，通过结构设计使其倾向于热 C(2)-C(6)/[2 + 2]环化模式，已被制备和表征，其中一个甚至通过 X 射线晶体学进行了表征。通过捕获实验和 DFT 计算，研究了它们转化为正规 [2 + 2] 环加成物的机制。结果支持涉及 C(2)-C(6) 二自由基中间体可逆形成的逐步机制。
相似文献
1
The thermal C2-C6/[2 + 2] cyclisation of enyne-allenes: reversible diradical formation.C2-C6 热 [2 + 2]环化反应：烯炔-allenes 的可逆自由基形成。
Org Biomol Chem. 2011 May 21;9(10):3776-9. doi: 10.1039/c0ob01275k. Epub 2011 Apr 12.
2
Thermal C2-C6 cyclization of enyne-allenes. Experimental evidence for a stepwise mechanism and for an unusual thermal silyl shift.烯炔丙二烯的热C2-C6环化反应。逐步反应机理及异常热硅基迁移的实验证据。
J Org Chem. 2007 Mar 16;72(6):2166-73. doi: 10.1021/jo062448+. Epub 2007 Feb 20.
3
Thermal C2-C6 cyclization of enyne-carbodiimides: experimental evidence contradicts a diradical and suggests a carbene intermediate.烯炔-碳二亚胺的热C2-C6环化反应：实验证据反驳了双自由基机理并表明存在卡宾中间体。
J Org Chem. 2008 Apr 18;73(8):3005-16. doi: 10.1021/jo701966h. Epub 2008 Mar 21.
4
Photochemical C2-C6 cyclization of enyne-allenes: detection of a fulvene triplet diradical in the laser flash photolysis.烯炔-丙二烯的光化学C2-C6环化反应：激光闪光光解中富烯三线态双自由基的检测
J Org Chem. 2008 Nov 21;73(22):8815-28. doi: 10.1021/jo801689w. Epub 2008 Oct 15.
5
Kinetic isotope effects in the thermal C2-C6 cyclization of enyne-allenes: experimental evidence supports a stepwise mechanism.烯炔-丙二烯热C2-C6环化反应中的动力学同位素效应：实验证据支持分步机理。
J Org Chem. 2005 Jun 10;70(12):4865-8. doi: 10.1021/jo0504971.
6
The photochemical C2-C6 cyclization of enyne-allenes: interception of the fulvene diradical with a radical clock ring opening.烯炔-allenes 的光化学 C2-C6 环化：富烯自由基与自由基钟开环的拦截。
J Org Chem. 2009 Aug 21;74(16):5850-60. doi: 10.1021/jo900439x.
7
Theoretical investigation of the photochemical C2-C6 cyclisation of enyne-heteroallenes.烯炔-杂联烯光化学C2-C6环化反应的理论研究
Chemistry. 2003 Oct 6;9(19):4670-7. doi: 10.1002/chem.200305001.
8
Nonstatistical dynamic effects in the thermal C2-C6 Diels-Alder cyclization of enyne-allenes.非统计动力学效应对烯炔-烯丙基的 C2-C6 Diels-Alder 环化反应的影响。
J Org Chem. 2013 Feb 15;78(4):1451-62. doi: 10.1021/jo302524a. Epub 2013 Feb 5.
9
Oxyanion-accelerated C2-C6 cyclization of benzannulated enyne-allenes.氧阴离子加速的苯并烯炔-联烯的C2-C6环化反应。
J Org Chem. 2000 Aug 25;65(17):5114-9. doi: 10.1021/jo991876v.
10
Nonstatistical dynamics in the thermal C2-C6/diels-alder cyclization of enyne-allenes: effect of topology.
J Org Chem. 2015 Feb 20;80(4):2174-81. doi: 10.1021/jo502693b. Epub 2015 Feb 3.
Zotero 插件