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在烯丙基碳上具有硅基取代的1-氮杂三烯的高度扭矩选择性电环化反应及竞争性的1,7-氢迁移反应

Highly torquoselective electrocyclizations and competing 1,7-hydrogen shifts of 1-azatrienes with silyl substitution at the allylic carbon.

作者信息

Ma Zhi-Xiong, Patel Ashay, Houk K N, Hsung Richard P

机构信息

†Division of Pharmaceutical Sciences, School of Pharmacy, and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53705, United States.

‡Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.

出版信息

Org Lett. 2015 May 1;17(9):2138-41. doi: 10.1021/acs.orglett.5b00727. Epub 2015 Apr 10.

DOI:10.1021/acs.orglett.5b00727
PMID:25859907
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4547485/
Abstract

Highly torquoselective electrocyclizations of chiral 1-azatrienes are described. These 1-azatrienes contain an allylic stereocenter that is substituted with a silyl group and are derived in situ from condensation of γ-silyl-substituted enals with vinylogous amides. The ensuing stereoselective ring closures are part of a tandem sequence that constitutes an aza-[3 + 3] annulation method for constructing 1,2-dihydropyridines. Several mechanisms for the formal 1,7-hydrogen shift of these 1-azatrienes were evaluated computationally.

摘要

描述了手性1-氮杂三烯的高度扭矩选择性电环化反应。这些1-氮杂三烯含有一个被硅烷基取代的烯丙基立体中心，并且是通过γ-硅烷基取代的烯醛与烯丙基酰胺的缩合原位衍生而来。随后的立体选择性环化是串联反应序列的一部分，该序列构成了一种用于构建1,2-二氢吡啶的氮杂-[3 + 3]环化方法。通过计算评估了这些1-氮杂三烯形式上的1,7-氢迁移的几种机理。

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1
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J Am Chem Soc. 2014 Jul 16;136(28):9802-5. doi: 10.1021/ja502252t. Epub 2014 Jul 3.
2
Intramolecular oxyallyl-carbonyl (3 + 2) cycloadditions.分子内氧杂烯丙基-羰基（3 + 2）环加成反应。
J Am Chem Soc. 2013 Apr 10;135(14):5242-5. doi: 10.1021/ja312459b. Epub 2013 Apr 1.
3
Control of regioselectivity and stereoselectivity in (4 + 3) cycloadditions of chiral oxyallyls with unsymmetrically disubstituted furans.手性氧杂丙二烯与不对称双取代呋喃的（4 + 3）环加成中区域选择性和立体选择性的控制。
J Org Chem. 2013 Mar 1;78(5):1753-9. doi: 10.1021/jo3011792. Epub 2012 Jul 31.
4
Stereoselectivities and regioselectivities of (4 + 3) cycloadditions between allenamide-derived chiral oxazolidinone-stabilized oxyallyls and furans: experiment and theory.手性噁唑烷酮稳定的氧杂丙烯与呋喃的（4 + 3）环加成的立体选择性和区域选择性：实验和理论。
J Am Chem Soc. 2011 Sep 14;133(36):14443-51. doi: 10.1021/ja205700p. Epub 2011 Aug 18.
5
[1,5]-H shift of aldehyde hydrogen in dienal compounds to produce ketenes.二烯醛化合物中醛氢的[1,5]-H 迁移生成烯酮。
Org Lett. 2011 Aug 19;13(16):4292-5. doi: 10.1021/ol2016302. Epub 2011 Jul 14.
6
Stereoselectivity in Oxyallyl-Furan 4+3 Cycloadditions: Control of Intermediate Conformations and Dispersive Stabilisation with Evans' Oxazolidinones.氧代烯丙基-呋喃4+3环加成反应中的立体选择性：利用伊文斯恶唑烷酮控制中间体构象和分散稳定作用
Chem Sci. 2010 Sep 1;1(3):387-392. doi: 10.1039/C0SC00280A.
7
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Org Lett. 2010 Dec 3;12(23):5506-9. doi: 10.1021/ol1023745. Epub 2010 Nov 4.
8
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Curr Org Synth. 2010 Aug 1;7(4):363-401. doi: 10.2174/157017910791414490.
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Tetrahedron. 2008 Jan 28;64(5):883-893. doi: 10.1016/j.tet.2007.09.089.
10
Torquoselective 6pi-electron electrocyclic ring closure of 1-azatrienes containing acyclic chirality at the C-terminus.C端含有无环手性的1-氮杂三烯的对旋选择性6π-电子电环化闭环反应。
Org Lett. 2006 Jun 8;8(12):2611-4. doi: 10.1021/ol060932t.