有氧 Pd 催化 sp3 C-H 双键形成反应：构建 N-杂环骨架和烯烃的新途径。
Aerobic Pd-catalyzed sp3 C-H olefination: a route to both N-heterocyclic scaffolds and alkenes.
机构信息
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, USA.
出版信息
J Am Chem Soc. 2011 May 4;133(17):6541-4. doi: 10.1021/ja2015586. Epub 2011 Apr 8.
Abstract
This communication describes a new method for the Pd/polyoxometalate-catalyzed aerobic olefination of unactivated sp(3) C-H bonds. Nitrogen heterocycles serve as directing groups, and air is used as the terminal oxidant. The products undergo reversible intramolecular Michael addition, which protects the monoalkenylated product from overfunctionalization. Hydrogenation of the Michael adducts provides access to bicyclic nitrogen-containing scaffolds that are prevalent in alkaloid natural products. Additionally, the cationic Michael adducts undergo facile elimination to release α,β-unsaturated olefins, which can be further elaborated via C-C and C-heteroatom bond-forming reactions.
摘要
本文描述了一种新的方法，用于 Pd/多金属氧酸盐催化的未活化 sp(3) C-H 键的有氧烯烃化反应。氮杂环作为导向基团，空气作为末端氧化剂。产物经历可逆的分子内迈克尔加成反应，从而保护单烯丙基化产物免受过度官能化。迈克尔加成产物的加氢反应提供了获得在生物碱天然产物中普遍存在的双环含氮支架的途径。此外，阳离子迈克尔加成物易于消除释放α,β-不饱和烯烃，这些烯烃可以通过 C-C 和 C-杂原子键形成反应进一步进行修饰。
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1
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2
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Chemistry. 2010 Oct 4;16(37):11212-22. doi: 10.1002/chem.201001363.
3
Cationic Pd(II)-catalyzed Fujiwara-Moritani reactions at room temperature in water.室温下水中的阳离子 Pd(II)催化的 Fujiwara-Moritani 反应。
Org Lett. 2010 May 7;12(9):1972-5. doi: 10.1021/ol100331h.
4
Pd(II)/HPMoV-catalyzed direct oxidative coupling reaction of benzenes with olefins.Pd(II)/HPMoV 催化的苯与烯烃的直接氧化偶联反应。
Molecules. 2010 Mar 9;15(3):1487-500. doi: 10.3390/molecules15031487.
5
Concise access to a model of the marine alkaloid halicyclamine A through macrocycle-forming addition of a 5-aminopenta-2,4-dienal onto a 2,3-dihydropyridinium salt.通过将5-氨基戊-2,4-二烯醛进行大环化加成到2,3-二氢吡啶盐上，简洁地获得海洋生物碱哈利环胺A的模型。
Chemistry. 2010 Mar 22;16(12):3594-7. doi: 10.1002/chem.201000142.
6
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7
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J Am Chem Soc. 2010 Mar 24;132(11):3965-72. doi: 10.1021/ja910900p.
8
Functionalization of organic molecules by transition-metal-catalyzed C(sp3)-H activation.过渡金属催化的 C(sp3)-H 活化官能团化有机分子。
Chemistry. 2010 Mar 1;16(9):2654-72. doi: 10.1002/chem.200902374.
9
Palladium-catalyzed ligand-directed C-H functionalization reactions.钯催化的配体导向碳氢键官能团化反应
Chem Rev. 2010 Feb 10;110(2):1147-69. doi: 10.1021/cr900184e.
10
O-acetyl oximes as transformable directing groups for Pd-catalyzed C-H bond functionalization.O-乙酰肟作为可转化的导向基团用于 Pd 催化的 C-H 键功能化反应。
Org Lett. 2010 Feb 5;12(3):532-5. doi: 10.1021/ol902720d.
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