超亲电试剂及三氟甲基取代基的影响。
Superelectrophiles and the effects of trifluoromethyl substituents.
作者信息
O'Connor Matthew J, Boblak Kenneth N, Topinka Michael J, Kindelin Patrick J, Briski Jason M, Zheng Chong, Klumpp Douglas A
机构信息
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115, USA.
出版信息
J Am Chem Soc. 2010 Mar 17;132(10):3266-7. doi: 10.1021/ja1001482.
Abstract
Trifluoromethyl-substituted superelectrophiles were generated in superacid (CF(3)SO(3)H), and their chemistry was examined. The strong electron-withdrawing properties of the trifluoromethyl group are found to enhance the electrophilic character at cationic sites in superelectrophiles. This leads to greater positive-charge delocalization in the superelectrophiles. These effects are manifested by the unusual chemo-, regio-, and stereoselectivities shown by the superelectrophiles in chemical reactions.
摘要
三氟甲基取代的超亲电试剂在超酸（CF(3)SO(3)H）中生成，并对其化学性质进行了研究。发现三氟甲基强大的吸电子特性增强了超亲电试剂阳离子位点的亲电特性。这导致超亲电试剂中出现更大程度的正电荷离域。这些效应表现为超亲电试剂在化学反应中展现出的异常化学选择性、区域选择性和立体选择性。
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1
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2
BF3-H2O catalyzed hydroxyalkylation of aromatics with aromatic aldehydes and dicarboxaldehydes: efficient synthesis of triarylmethanes, diarylmethylbenzaldehydes, and anthracene derivatives.BF3·H2O 催化的芳香醛和二醛与芳香族化合物的羟烷基化反应：三芳基甲烷、二芳基甲基苯甲醛和蒽衍生物的有效合成。
J Org Chem. 2009 Nov 20;74(22):8659-68. doi: 10.1021/jo901668j.
3
Evidence for pi-stacking as a source of stereocontrol in the synthesis of the core pyranochromene ring system common to calyxin I, calyxin J, and epicalyxin J.在合成萼花素I、萼花素J和表萼花素J共有的核心吡喃并色烯环系统中，π-堆积作为立体控制来源的证据。
J Org Chem. 2009 Oct 2;74(19):7529-32. doi: 10.1021/jo901436u.
4
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J Am Chem Soc. 2007 Feb 14;129(6):1724-32. doi: 10.1021/ja067682w. Epub 2007 Jan 24.
5
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Chem Rev. 1997 Aug 5;97(5):1303-1324. doi: 10.1021/cr9603744.
6
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7
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