钯催化通过串联定向碳钯化/C-H键官能团化合成环戊烷稠合苯并环丁烯
Palladium-catalyzed synthesis of cyclopentane-fused benzocyclobutenes via tandem directed carbopalladation/C-H bond functionalization.
作者信息
Bertrand Myra Beaudoin, Wolfe John P
机构信息
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109-1055, USA.
出版信息
Org Lett. 2007 Aug 2;9(16):3073-5. doi: 10.1021/ol071120f. Epub 2007 Jul 7.
Abstract
A new Pd-catalyzed reaction for the stereoselective synthesis of cyclopentane-fused benzocyclobutenes is described. These transformations likely proceed via carbamate-directed carbopalladation followed by intramolecular C-H activation of an alkylpalladium intermediate. The mechanistic relationship between these transformations and Pd-catalyzed reactions of gamma-(n-Boc-amino)alkenes with aryl bromides that afford pyrrolidines is discussed. Differences in reactivity between Pd-amino and Pd-amido complexes appear to play a key role in the outcome of these transformations.
摘要
本文描述了一种用于立体选择性合成环戊烷稠合苯并环丁烯的新型钯催化反应。这些转化可能通过氨基甲酸酯导向的碳钯化反应，随后对烷基钯中间体进行分子内C-H活化来进行。讨论了这些转化与钯催化的γ-（N-叔丁氧羰基氨基）烯烃与芳基溴反应生成吡咯烷之间的机理关系。钯-氨基和钯-酰胺配合物之间的反应性差异似乎在这些转化的结果中起着关键作用。
相似文献
1
Palladium-catalyzed synthesis of cyclopentane-fused benzocyclobutenes via tandem directed carbopalladation/C-H bond functionalization.钯催化通过串联定向碳钯化/C-H键官能团化合成环戊烷稠合苯并环丁烯
Org Lett. 2007 Aug 2;9(16):3073-5. doi: 10.1021/ol071120f. Epub 2007 Jul 7.
2
Palladium-Catalyzed Double C-H Functionalization of Arenes at the Positions ortho and meta to Their Directing Group: Concise Synthesis of Benzocyclobutenes.钯催化芳烃在其导向基团邻位和间位的双C-H官能化反应：苯并环丁烯的简洁合成
Chem Pharm Bull (Tokyo). 2016;64(9):1384-92. doi: 10.1248/cpb.c16-00439.
3
Pd-catalyzed intramolecular acylation of aryl bromides via C-H functionalization: a highly efficient synthesis of benzocyclobutenones.钯催化的芳基溴化物通过 C-H 功能化的分子内酰化反应：苯并环丁烯酮的高效合成。
J Am Chem Soc. 2010 Jan 20;132(2):466-7. doi: 10.1021/ja909811t.
4
Pd-Catalyzed Alkene Difunctionalization Reactions of Malonate Nucleophiles: Synthesis of Substituted Cyclopentanes via Alkene Aryl-Alkylation and Akenyl-Alkylation.钯催化的丙二酸酯亲核试剂的烯烃双官能化反应：通过烯烃芳基烷基化和烯基烷基化合成取代的环戊烷。
Org Lett. 2019 May 17;21(10):3813-3816. doi: 10.1021/acs.orglett.9b01258. Epub 2019 Apr 25.
5
Palladium-catalyzed synthesis of 2,1'-disubstituted tetrahydrofurans from gamma-hydroxy internal alkenes. Evidence for alkene insertion into a Pd-O bond and stereochemical scrambling via beta-hydride elimination.钯催化由γ-羟基内烯烃合成2,1'-二取代四氢呋喃。烯烃插入钯-氧键及通过β-氢消除实现立体化学混乱的证据。
J Am Chem Soc. 2005 Nov 30;127(47):16468-76. doi: 10.1021/ja054754v.
6
Synthesis of polycyclic nitrogen heterocycles via alkene aminopalladation/carbopalladation cascade reactions.通过烯烃氨钯化/碳钯化级联反应合成多环氮杂环。
Org Lett. 2010 Mar 5;12(5):1028-31. doi: 10.1021/ol100033s.
7
Pd-catalyzed alkyl to aryl migration and cyclization: an efficient synthesis of fused polycycles via multiple C-H activation.钯催化的烷基到芳基迁移和环化：通过多次碳氢键活化高效合成稠合多环化合物
J Am Chem Soc. 2004 Jun 23;126(24):7460-1. doi: 10.1021/ja047980y.
8
Modular Synthesis of Benzocyclobutenes via Pd(II)-Catalyzed Oxidative [2+2] Annulation of Arylboronic Acids with Alkenes.通过钯（II）催化的芳基硼酸与烯烃的氧化[2+2]环加成反应合成苯并环丁烯。
J Am Chem Soc. 2022 May 25;144(20):8920-8926. doi: 10.1021/jacs.2c03565. Epub 2022 May 13.
9
Synthesis of Polycyclic Nitrogen Heterocycles via Cascade Pd-Catalyzed Alkene Carboamination/Diels-Alder Reactions.通过串联钯催化的烯烃碳胺化/狄尔斯-阿尔德反应合成多环氮杂环化合物
Org Lett. 2015 May 15;17(10):2378-81. doi: 10.1021/acs.orglett.5b00896. Epub 2015 May 6.
10
An entry to vinylcyclopropane through palladium-catalyzed intramolecular cyclopropanation of alkenes with unstabilized allylic tosylhydrazones.通过钯催化的烯烃与不稳定烯丙基对甲苯磺酰腙的分子内环丙烷化反应制备乙烯基环丙烷。
Chem Commun (Camb). 2015 Apr 11;51(28):6179-82. doi: 10.1039/c5cc00235d.
引用本文的文献
1
Mechanistic Studies of Azaphilic versus Carbophilic Activation by Gold(I) in the Gold/Palladium Dual-Catalyzed Rearrangement of Alkenyl Vinyl Aziridines.金/钯双催化烯基乙烯基氮丙啶重排反应中，金（I）对亲氮与亲碳活化作用的机理研究
Organometallics. 2012 Oct 8;31(19):6843-6850. doi: 10.1021/om300671j.
2
Stereoselective Synthesis of Saturated Heterocycles via Pd-Catalyzed Alkene Carboetherification and Carboamination Reactions.通过钯催化的烯烃碳醚化和碳胺化反应立体选择性合成饱和杂环化合物。
Synlett. 2006 Nov 13;2007(4):571-582. doi: 10.1002/ejoc.200600767.
3
Mild conditions for Pd-catalyzed carboamination of N-protected hex-4-enylamines and 1-, 3-, and 4-substituted pent-4-enylamines. Scope, limitations, and mechanism of pyrrolidine formation.钯催化的N-保护己-4-烯基胺和1-、3-及4-取代戊-4-烯基胺的碳胺化反应的温和条件。吡咯烷形成的范围、局限性及机理。
J Org Chem. 2008 Nov 21;73(22):8851-60. doi: 10.1021/jo801631v. Epub 2008 Oct 23.
本文引用的文献
1
Effects of Bases and Halides on the Amination of Chloroarenes Catalyzed by Pd(PBu).碱和卤化物对钯（三丁基膦）催化氯代芳烃胺化反应的影响
Organometallics. 2007 Jan 15;26(2):340-351. doi: 10.1021/om0607548. Epub 2006 Dec 19.
2
3
Mild conditions for the synthesis of functionalized pyrrolidines via Pd-catalyzed carboamination reactions.通过钯催化的碳胺化反应合成官能化吡咯烷的温和条件。
Org Lett. 2007 Feb 1;9(3):457-60. doi: 10.1021/ol062808f.
4
Domino Heck-C-H activation reaction of unsymmetrically substituted [3]cumulene.不对称取代的[3]累积烯的多米诺 Heck-C-H 活化反应。
Chem Commun (Camb). 2006 Sep 14(34):3648-50. doi: 10.1039/b607684j. Epub 2006 Aug 3.
5
Synthesis of 3-(diarylmethylenyl)oxindole by a palladium-catalyzed domino carbopalladation/C-H activation/C-C bond-forming process.通过钯催化的多米诺碳钯化/C-H活化/C-C键形成过程合成3-(二芳基亚甲基)氧化吲哚
Org Lett. 2006 Oct 12;8(21):4927-30. doi: 10.1021/ol062022h.
6
A concise stereoselective synthesis of Preussin, 3-epi-Preussin, and analogues.普瑞辛、3-表普瑞辛及其类似物的简洁立体选择性合成。
Org Lett. 2006 May 25;8(11):2353-6. doi: 10.1021/ol0606435.
7
Palladium-catalyzed direct arylation of simple arenes in synthesis of biaryl molecules.钯催化简单芳烃在联芳基分子合成中的直接芳基化反应。
Chem Commun (Camb). 2006 Mar 28(12):1253-64. doi: 10.1039/b515481m. Epub 2006 Jan 30.
8
Selective synthesis of 5- or 6-aryl octahydrocyclopenta[b]pyrroles from a common precursor through control of competing pathways in a Pd-catalyzed reaction.通过在钯催化反应中控制竞争途径，从共同前体选择性合成5-或6-芳基八氢环戊并[b]吡咯。
J Am Chem Soc. 2005 Jun 22;127(24):8644-51. doi: 10.1021/ja0430346.
9
Study of a new rate increasing "base effect" in the palladium-catalyzed amination of aryl iodides.钯催化芳基碘胺化反应中新型速率增加“基效应”的研究
J Org Chem. 2004 Sep 3;69(18):6010-7. doi: 10.1021/jo049774e.
10
Palladium-catalyzed synthesis of N-aryl pyrrolidines from gamma-(N-Arylamino) alkenes: evidence for chemoselective alkene insertion into Pd--N bonds.钯催化由γ-（N-芳基氨基）烯烃合成N-芳基吡咯烷：化学选择性烯烃插入钯-氮键的证据
Angew Chem Int Ed Engl. 2004 Jul 5;43(27):3605-8. doi: 10.1002/anie.200460060.
Zotero 插件