芳基氯作为亲电试剂在 Pd 催化的烯烃双官能团化反应中的应用。
Use of aryl chlorides as electrophiles in Pd-catalyzed alkene difunctionalization reactions.
机构信息
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109-1055, USA.
出版信息
J Org Chem. 2010 Apr 16;75(8):2756-9. doi: 10.1021/jo100344k.
Abstract
The development of conditions that allow use of inexpensive aryl chlorides as electrophiles in Pd-catalyzed alkene carboamination and carboetherification reactions is described. A catalyst composed of Pd(OAc)(2) and S-Phos minimizes N-arylation of the substrate and prevents formation of mixtures of regioisomeric products. A number of heterocycles, including pyrrolidines, isoxazolidines, tetrahydrofurans, and pyrazolidines, are efficiently generated with this method.
摘要
描述了一种条件的发展，该条件允许在 Pd 催化的烯属碳氨化和碳醚化反应中使用廉价的芳基氯作为亲电试剂。由 Pd(OAc)(2)和 S-Phos 组成的催化剂最大限度地减少了底物的 N-芳基化，并防止了区域异构产物混合物的形成。该方法可有效地生成多种杂环化合物，包括吡咯烷、异噁唑烷、四氢呋喃和吡唑烷。
相似文献
1
Use of aryl chlorides as electrophiles in Pd-catalyzed alkene difunctionalization reactions.
J Org Chem. 2010 Apr 16;75(8):2756-9. doi: 10.1021/jo100344k.
2
Influence of catalyst structure and reaction conditions on anti- versus syn-aminopalladation pathways in Pd-catalyzed alkene carboamination reactions of N-allylsulfamides.
Chemistry. 2014 Jul 7;20(28):8782-90. doi: 10.1002/chem.201402258. Epub 2014 Jun 17.
3
Highly diastereoselective Pd-catalyzed carboetherification reactions of acyclic internal alkenes. Stereoselective synthesis of polysubstituted tetrahydrofurans.
Org Lett. 2010 Mar 19;12(6):1268-71. doi: 10.1021/ol1001472.
4
Asymmetric Palladium-Catalyzed Alkene Carboamination Reactions for the Synthesis of Cyclic Sulfamides.
Chemistry. 2016 Apr 18;22(17):5919-22. doi: 10.1002/chem.201600887. Epub 2016 Mar 10.
5
Stereoselective Synthesis of Saturated Heterocycles via Pd-Catalyzed Alkene Carboetherification and Carboamination Reactions.
Synlett. 2006 Nov 13;2007(4):571-582. doi: 10.1002/ejoc.200600767.
6
Synthesis of Substituted γ- and δ-Lactams via Pd-Catalyzed Alkene Carboamination Reactions.
J Org Chem. 2017 Mar 3;82(5):2777-2786. doi: 10.1021/acs.joc.7b00041. Epub 2017 Feb 23.
7
Intramolecular alkene carboamination reactions for the synthesis of enantiomerically enriched tropane derivatives.
Org Lett. 2011 Jun 3;13(11):2962-5. doi: 10.1021/ol201051q. Epub 2011 May 11.
8
Stereocontrolled synthesis of bicyclic sulfamides via Pd-catalyzed alkene carboamination reactions. Control of 1,3-asymmetric induction by manipulating mechanistic pathways.
Org Lett. 2014 Jun 20;16(12):3412-5. doi: 10.1021/ol5015976. Epub 2014 Jun 11.
9
Asymmetric Pd-Catalyzed Alkene Carboamination Reactions for the Synthesis of 2-Aminoindane Derivatives.
J Am Chem Soc. 2015 Sep 9;137(35):11246-9. doi: 10.1021/jacs.5b07203. Epub 2015 Aug 27.
10
Intramolecular Pd-catalyzed carboetherification and carboamination. Influence of catalyst structure on reaction mechanism and product stereochemistry.
J Am Chem Soc. 2006 Mar 8;128(9):2893-901. doi: 10.1021/ja057489m.
引用本文的文献
1
Allylation of isatin-derived N-Boc-hydrazones followed by Pd-catalyzed carboamination reaction: an entry to 3-spiro-pyrazolidyl-oxindoles.
RSC Adv. 2019 Nov 20;9(65):37788-37800. doi: 10.1039/c9ra07712j. eCollection 2019 Nov 19.
2
Palladium/Xu-Phos-catalyzed asymmetric carboamination towards isoxazolidines and pyrrolidines.
Chem Sci. 2021 May 5;12(23):8241-8245. doi: 10.1039/d1sc01337h.
3
Catalyst-free carbosilylation of alkenes using silyl boronates and organic fluorides via selective C-F bond activation.
Nat Commun. 2021 Jun 18;12(1):3749. doi: 10.1038/s41467-021-24031-w.
4
Recent Developments in Pd-Catalyzed Alkene Aminoarylation Reactions for the Synthesis of Nitrogen Heterocycles.
Synthesis (Stuttg). 2012;44(3):351-361. doi: 10.1055/s-0031-1289668.
5
Combined oxypalladation/C-H functionalization: palladium(II)-catalyzed intramolecular oxidative oxyarylation of hydroxyalkenes.
Angew Chem Int Ed Engl. 2012 Feb 20;51(8):1926-9. doi: 10.1002/anie.201108129. Epub 2012 Jan 11.
6
Intercepting Wacker intermediates with arenes: C-H functionalization and dearomatization.
Org Lett. 2011 Dec 2;13(23):6320-3. doi: 10.1021/ol202881q. Epub 2011 Nov 9.
7
Cascade intramolecular N-arylation/intermolecular carboamination reactions for the construction of tricyclic heterocycles.
Org Lett. 2011 Jun 17;13(12):3218-21. doi: 10.1021/ol201123b. Epub 2011 May 23.
8
Intramolecular alkene carboamination reactions for the synthesis of enantiomerically enriched tropane derivatives.
Org Lett. 2011 Jun 3;13(11):2962-5. doi: 10.1021/ol201051q. Epub 2011 May 11.
本文引用的文献
1
Palladium-catalyzed alkene carboamination reactions for the synthesis of substituted piperazines.
Tetrahedron. 2009 Sep 15;65(33):6549-6570. doi: 10.1016/j.tet.2009.04.017.
2
Palladium-Catalyzed Carboetherification and Carboamination Reactions of γ-Hydroxy- and γ-Aminoalkenes for the Synthesis of Tetrahydrofurans and Pyrrolidines.
European J Org Chem. 2007 Feb;2007(4):571-582.
3
Highly diastereoselective Pd-catalyzed carboetherification reactions of acyclic internal alkenes. Stereoselective synthesis of polysubstituted tetrahydrofurans.
Org Lett. 2010 Mar 19;12(6):1268-71. doi: 10.1021/ol1001472.
4
Diastereoselective synthesis of hexahydro-3H-pyrrolyzin-3-ones through Pd-catalyzed carboamination.
J Org Chem. 2010 Mar 19;75(6):2134-7. doi: 10.1021/jo1002032.
5
Homogeneous gold-catalyzed oxidative carboheterofunctionalization of alkenes.
J Am Chem Soc. 2010 Feb 10;132(5):1474-5. doi: 10.1021/ja909555d.
6
A concise palladium-catalyzed carboamination route to (+/-)-tylophorine.
J Org Chem. 2009 Dec 18;74(24):9554-7. doi: 10.1021/jo902114u.
7
Mechanism of N-fluorobenzenesulfonimide promoted diamination and carboamination reactions: divergent reactivity of a Pd(IV) species.
J Am Chem Soc. 2009 Nov 4;131(43):15945-51. doi: 10.1021/ja906915w.
8
Synthesis of aziridines by palladium-catalyzed reactions of allylamines with aryl and alkenyl halides: evidence of a syn-carboamination pathway.
Angew Chem Int Ed Engl. 2009;48(39):7224-6. doi: 10.1002/anie.200903178.
9
Palladium-catalyzed carboamination of alkenes promoted by N-fluorobenzenesulfonimide via C-H activation of arenes.
J Am Chem Soc. 2009 Jul 15;131(27):9488-9. doi: 10.1021/ja9031659.
10
New strategy for the synthesis of substituted morpholines.
J Org Chem. 2009 Jul 17;74(14):5107-10. doi: 10.1021/jo9007223.
Zotero 插件