用于铑（III）催化C-H活化的改进催化剂结构及其在吡啶酮合成中的应用
An Improved Catalyst Architecture for Rhodium (III) Catalyzed C-H Activation and its Application to Pyridone Synthesis.
作者信息
Hyster Todd K, Rovis Tomislav
机构信息
Department of Chemistry, Fort Collins, CO 80523. Tel: 970-491-7208.
出版信息
Chem Sci. 2011 Aug 1;2(8):1606-1610. doi: 10.1039/C1SC00235J.
Abstract
We have developed a method for preparing pyridones from the coupling reaction of acrylamides and alkynes with either stoichometric Cu(OAc) or catalytic Cu(OAc) and air as oxidants. In the course of these studies, it was found that a larger ligand, 1,3-di-tert-butylcyclopentadienyl (termed Cp) results in higher degrees of regioselectivity in the alkyne insertion event. The transformation tolerates a broad variety of alkynes and acrylamides. Furthermore, Cp and Cp* demonstrate similar catalytic activity. This similarity allows for mechanistic studies to be undertaken which suggest a difference in mechanism between this reaction and the previously studied benzamide system.
摘要
我们已经开发出一种方法，可通过丙烯酰胺与炔烃的偶联反应，以化学计量的醋酸铜或催化量的醋酸铜并以空气作为氧化剂来制备吡啶酮。在这些研究过程中，发现一种更大的配体，即1,3-二叔丁基环戊二烯基（称为Cp），在炔烃插入反应中会导致更高程度的区域选择性。该转化反应能耐受多种炔烃和丙烯酰胺。此外，Cp和Cp*表现出相似的催化活性。这种相似性使得能够进行机理研究，结果表明该反应与之前研究的苯甲酰胺体系在机理上存在差异。
相似文献
1
An Improved Catalyst Architecture for Rhodium (III) Catalyzed C-H Activation and its Application to Pyridone Synthesis.用于铑（III）催化C-H活化的改进催化剂结构及其在吡啶酮合成中的应用
Chem Sci. 2011 Aug 1;2(8):1606-1610. doi: 10.1039/C1SC00235J.
2
Synthesis of 2-pyridones and iminoesters via Rh(III)-catalyzed oxidative coupling between acrylamides and alkynes.通过 Rh(III)催化的丙烯酰胺和炔烃之间的氧化偶联反应合成 2-吡啶酮和亚氨基酯。
Org Lett. 2010 Dec 3;12(23):5462-5. doi: 10.1021/ol102306c. Epub 2010 Oct 29.
3
Mechanism of Rhodium-Catalyzed C-H Functionalization: Advances in Theoretical Investigation.铑催化 C-H 功能化反应的机理：理论研究进展。
Acc Chem Res. 2017 Nov 21;50(11):2799-2808. doi: 10.1021/acs.accounts.7b00400. Epub 2017 Nov 7.
4
Computational Characterization of the Mechanism for the Oxidative Coupling of Benzoic Acid and Alkynes by Rhodium/Copper and Rhodium/Silver Systems.通过铑/铜和铑/银体系对苯甲酸和炔烃的氧化偶联反应机理的计算研究。
Chemistry. 2018 Aug 22;24(47):12383-12388. doi: 10.1002/chem.201800627. Epub 2018 Apr 25.
5
Direct Regio- and Diastereoselective Synthesis of δ-Lactams from Acrylamides and Unactivated Alkenes Initiated by Rh -Catalyzed C-H Activation.铑催化 C-H 活化引发的丙烯酰胺与非活化烯烃的 δ-内酰胺的区域和立体选择性直接合成。
Angew Chem Int Ed Engl. 2020 Mar 16;59(12):4965-4969. doi: 10.1002/anie.201916332. Epub 2020 Feb 11.
6
Divergent rhodium-catalyzed electrochemical vinylic C-H annulation of acrylamides with alkynes.铑催化的电化学丙烯酰胺与炔烃发散型 vinylic C-H 环化反应。
Nat Commun. 2021 Feb 10;12(1):930. doi: 10.1038/s41467-021-21190-8.
7
Oxidative C-H Activation Approach to Pyridone and Isoquinolone through an Iron-Catalyzed Coupling of Amides with Alkynes.通过铁催化酰胺与炔烃的偶联反应实现吡啶酮和异喹啉酮的氧化C-H活化方法
Chem Asian J. 2016 Feb 4;11(3):380-4. doi: 10.1002/asia.201501095. Epub 2015 Nov 4.
8
Rhodium-catalyzed oxidative cycloaddition of benzamides and alkynes via C-H/N-H activation.铑催化的通过 C-H/N-H 活化的苯甲酰胺和炔烃的氧化环加成反应。
J Am Chem Soc. 2010 Aug 4;132(30):10565-9. doi: 10.1021/ja103776u.
9
DFT Mechanistic Study of Rh(III)-Catalyzed [3 + 2]/[5 + 2] Annulation of 4-Aryl-1,2,3-triazoles and Alkynes Unveils the Dual C-H Activation Strategy.DFT 机理研究揭示了 Rh(III)催化的 4-芳基-1,2,3-三唑和炔烃的[3 + 2]/[5 + 2]环化反应的双重 C-H 活化策略。
J Org Chem. 2016 Oct 21;81(20):9639-9646. doi: 10.1021/acs.joc.6b01706. Epub 2016 Oct 12.
10
Switchable Regioselective C-H Activation/Annulation of Acrylamides with Alkynes for the Synthesis of 2-Pyridones.用于合成2-吡啶酮的丙烯酰胺与炔烃的可切换区域选择性C-H活化/环化反应
ChemSusChem. 2024 Oct 7;17(19):e202400066. doi: 10.1002/cssc.202400066. Epub 2024 May 23.
引用本文的文献
1
Rhodium-NHC-Catalyzed gem-Specific O-Selective Hydropyridonation of Terminal Alkynes.铑-氮杂环卡宾催化的末端炔烃的偕位特异性O-选择性氢吡啶化反应
Angew Chem Int Ed Engl. 2022 May 9;61(20):e202117006. doi: 10.1002/anie.202117006. Epub 2022 Mar 19.
2
Divergent rhodium-catalyzed electrochemical vinylic C-H annulation of acrylamides with alkynes.铑催化的电化学丙烯酰胺与炔烃发散型 vinylic C-H 环化反应。
Nat Commun. 2021 Feb 10;12(1):930. doi: 10.1038/s41467-021-21190-8.
3
A General and Highly Selective Palladium-Catalyzed Hydroamidation of 1,3-Diynes.钯催化 1,3-二炔的通用且高选择性氢酰胺化反应。
Angew Chem Int Ed Engl. 2021 Jan 4;60(1):371-379. doi: 10.1002/anie.202010768. Epub 2020 Oct 27.
4
Rhodium(i)-catalyzed C6-selective C-H alkenylation and polyenylation of 2-pyridones with alkenyl and conjugated polyenyl carboxylic acids.铑（I）催化2-吡啶酮与烯基和共轭多烯基羧酸的C6选择性C-H烯基化和多烯基化反应。
Chem Sci. 2019 Sep 9;10(43):10089-10096. doi: 10.1039/c9sc03672e. eCollection 2019 Nov 21.
5
Direct Regio- and Diastereoselective Synthesis of δ-Lactams from Acrylamides and Unactivated Alkenes Initiated by Rh -Catalyzed C-H Activation.铑催化 C-H 活化引发的丙烯酰胺与非活化烯烃的 δ-内酰胺的区域和立体选择性直接合成。
Angew Chem Int Ed Engl. 2020 Mar 16;59(12):4965-4969. doi: 10.1002/anie.201916332. Epub 2020 Feb 11.
6
Computational Study of the Ni-Catalyzed C-H Oxidative Cycloaddition of Aromatic Amides with Alkynes.镍催化芳酰胺与炔烃的C-H氧化环加成反应的计算研究
ACS Omega. 2019 Mar 13;4(3):5209-5220. doi: 10.1021/acsomega.9b00030. eCollection 2019 Mar 31.
7
Mild complexation protocol for chiral CpRh and Ir complexes suitable for catalysis.适用于催化的手性CpRh和Ir配合物的温和络合方案。
Chem Sci. 2018 Oct 31;10(3):781-787. doi: 10.1039/c8sc04385j. eCollection 2019 Jan 21.
8
Carbonyl-assisted reverse regioselective cascade annulation of 2-acetylenic ketones triggered by Ru-catalyzed C-H activation.钌催化的C-H活化引发的2-炔酮的羰基辅助反向区域选择性串联环化反应。
Chem Sci. 2016 Jul 1;7(7):4748-4753. doi: 10.1039/c6sc01456a. Epub 2016 Apr 12.
9
Rhodium-catalyzed C-H functionalization-based approach to eight-membered lactams.基于铑催化碳氢键官能团化的八元内酰胺合成方法
Chem Sci. 2015 Apr 1;6(4):2275-2285. doi: 10.1039/c5sc00092k. Epub 2015 Feb 5.
10
Electronic and Steric Tuning of a Prototypical Piano Stool Complex: Rh(III) Catalysis for C-H Functionalization.电子和空间效应对典型钢琴凳配合物的调谐：Rh(III)催化的 C-H 官能化反应。
Acc Chem Res. 2018 Jan 16;51(1):170-180. doi: 10.1021/acs.accounts.7b00444. Epub 2017 Dec 22.
本文引用的文献
1
Rhodium(III)-catalyzed heterocycle synthesis using an internal oxidant: improved reactivity and mechanistic studies.铑(III)催化的使用内部氧化剂的杂环合成：改进的反应性和机理研究。
J Am Chem Soc. 2011 Apr 27;133(16):6449-57. doi: 10.1021/ja201143v. Epub 2011 Mar 31.
2
Oxidative coupling of NH isoquinolones with olefins catalyzed by Rh(III).铑(III)催化 NH 异喹啉与烯烃的氧化偶联。
J Org Chem. 2011 Apr 15;76(8):2926-32. doi: 10.1021/jo2002209. Epub 2011 Mar 17.
3
The vinyl moiety as a handle for regiocontrol in the preparation of unsymmetrical 2,3-aliphatic-substituted indoles and pyrroles.乙烯基部分作为在制备不对称2,3-脂肪族取代吲哚和吡咯时用于区域控制的手柄。
Angew Chem Int Ed Engl. 2011 Feb 7;50(6):1338-41. doi: 10.1002/anie.201006381. Epub 2010 Dec 29.
4
Rh(III)-catalyzed directed C-H olefination using an oxidizing directing group: mild, efficient, and versatile.铑（III）催化的使用氧化导向基团的导向 C-H 烯化反应：温和、高效、多功能。
J Am Chem Soc. 2011 Mar 2;133(8):2350-3. doi: 10.1021/ja109676d. Epub 2011 Jan 28.
5
Rhodium-catalyzed oxidative olefination of C-H bonds in acetophenones and benzamides.铑催化苯乙酮和苯甲酰胺中C-H键的氧化烯基化反应。
Angew Chem Int Ed Engl. 2011 Feb 1;50(5):1064-7. doi: 10.1002/anie.201006222. Epub 2010 Dec 22.
6
Diverse strategies toward indenol and fulvene derivatives: Rh-catalyzed C-H activation of aryl ketones followed by coupling with internal alkynes.吲哚和富烯衍生物的多样化策略：铑催化的芳基酮 C-H 活化，然后与内部炔烃偶联。
J Am Chem Soc. 2011 Feb 23;133(7):2154-6. doi: 10.1021/ja110650m. Epub 2011 Jan 25.
7
Rhodium-catalyzed oxidative 1:1, 1:2, and 1:4 coupling reactions of phenylazoles with internal alkynes through the regioselective cleavages of multiple C-H bonds.铑催化的通过多个 C-H 键的区域选择性断裂实现的苯并唑与内部炔烃的 1:1、1:2 和 1:4 氧化偶联反应。
J Org Chem. 2011 Jan 7;76(1):13-24. doi: 10.1021/jo1021184. Epub 2010 Dec 8.
8
Rhodium(III)-catalyzed arene and alkene C-H bond functionalization leading to indoles and pyrroles.铑(III)催化芳环和烯烃 C-H 键功能化生成吲哚和吡咯。
J Am Chem Soc. 2010 Dec 29;132(51):18326-39. doi: 10.1021/ja1082624. Epub 2010 Dec 6.
9
Rh(III)-catalyzed tandem oxidative olefination-Michael reactions between aryl carboxamides and alkenes.铱(III)催化的芳基甲酰胺和烯烃之间的串联氧化烯烃化-Michael 反应。
Org Lett. 2010 Dec 3;12(23):5430-3. doi: 10.1021/ol102241f. Epub 2010 Nov 1.
10
Synthesis of 2-pyridones and iminoesters via Rh(III)-catalyzed oxidative coupling between acrylamides and alkynes.通过 Rh(III)催化的丙烯酰胺和炔烃之间的氧化偶联反应合成 2-吡啶酮和亚氨基酯。
Org Lett. 2010 Dec 3;12(23):5462-5. doi: 10.1021/ol102306c. Epub 2010 Oct 29.
Zotero 插件