手性双功能N-杂环卡宾配体的合成及其在不对称金催化中的应用研究
Synthesis of Chiral Bifunctional NHC Ligands and Survey of Their Utilities in Asymmetric Gold Catalysis.
作者信息
Zhang Jun-Qi, Liu Yunkui, Wang Xing-Wang, Zhang Liming
机构信息
Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States.
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China.
出版信息
Organometallics. 2019 Aug 5;38(20):3931-3938. doi: 10.1021/acs.organomet.9b00400. Epub 2019 Oct 28.
Abstract
The synthesis and characterization of the chiral bifunctional NHC ligands based on the imidazo[1,5-]pyridine (ImPy) scaffold are described. These ligands possess a fluxional biaryl axis and a chiral center. The configurational stability of the biaryl axis in their gold(I) complexes is investigated. The application of these axially chiral ImPy-based AuCl complexes in a series of gold catalysis is explored, and varying degrees of asymmetric induction are observed. In most cases, the ligand (a)- with its cyclohexyl group pointing to the reaction site and hence exerting asymmetric steric influence is more effective in asymmetric induction.
摘要
描述了基于咪唑并[1,5 -]吡啶（ImPy）骨架的手性双功能NHC配体的合成与表征。这些配体具有一个可旋转的联芳基轴和一个手性中心。研究了它们的金（I）配合物中联芳基轴的构型稳定性。探索了这些基于轴手性ImPy的AuCl配合物在一系列金催化反应中的应用，并观察到了不同程度的不对称诱导作用。在大多数情况下，配体（a）——其环己基指向反应位点并因此施加不对称空间影响——在不对称诱导方面更有效。
相似文献
1
Synthesis of Chiral Bifunctional NHC Ligands and Survey of Their Utilities in Asymmetric Gold Catalysis.
Organometallics. 2019 Aug 5;38(20):3931-3938. doi: 10.1021/acs.organomet.9b00400. Epub 2019 Oct 28.
2
Chiral ditopic cyclophosphazane (CycloP) ligands: synthesis, coordination chemistry, and application in asymmetric catalysis.
Chemistry. 2013 Oct 4;19(41):13823-37. doi: 10.1002/chem.201302327. Epub 2013 Aug 28.
3
Chiral Bifunctional Phosphine Ligand Enabling Gold-Catalyzed Asymmetric Isomerization of Alkyne to Allene and Asymmetric Synthesis of 2,5-Dihydrofuran.
J Am Chem Soc. 2019 Mar 6;141(9):3787-3791. doi: 10.1021/jacs.8b12833. Epub 2019 Feb 21.
4
Gold-Catalyzed Desymmetric Lactonization of Alkynylmalonic Acids Enabled by Chiral Bifunctional P,N ligands.
Angew Chem Int Ed Engl. 2022 Jun 7;61(23):e202201739. doi: 10.1002/anie.202201739. Epub 2022 Apr 5.
5
Chiral Bidentate NHC Ligands Based on the 1,1'-Binaphthyl Scaffold: Synthesis and Application in Transition-Metal-Catalyzed Asymmetric Reactions.
Chem Rec. 2016 Dec;16(6):2736-2749. doi: 10.1002/tcr.201600103. Epub 2016 Sep 26.
6
Synthesis of axially chiral gold complexes and their applications in asymmetric catalyses.
Beilstein J Org Chem. 2013 Oct 28;9:2224-32. doi: 10.3762/bjoc.9.261. eCollection 2013.
7
Helical Chiral N-Heterocyclic Carbene Ligands in Enantioselective Gold Catalysis.
Chemistry. 2022 Mar 22;28(17):e202200166. doi: 10.1002/chem.202200166. Epub 2022 Feb 28.
8
Chiral Pd-Catalyzed Enantioselective Syntheses of Various N-C Axially Chiral Compounds and Their Synthetic Applications.
Acc Chem Res. 2021 Feb 2;54(3):719-730. doi: 10.1021/acs.accounts.0c00767. Epub 2021 Jan 22.
9
Synthesis and Application of Chiral Spiro Cp Ligands in Rhodium-Catalyzed Asymmetric Oxidative Coupling of Biaryl Compounds with Alkenes.
J Am Chem Soc. 2016 Apr 27;138(16):5242-5. doi: 10.1021/jacs.6b02302. Epub 2016 Apr 15.
10
New Approaches for Biaryl-Based Phosphine Ligand Synthesis via P═O Directed C-H Functionalizations.
Acc Chem Res. 2017 Jun 20;50(6):1480-1492. doi: 10.1021/acs.accounts.7b00167. Epub 2017 May 9.
引用本文的文献
1
Bifunctional Chiral ImPy-Carbene Ligands. H-Bonding Controlled Reactivity and Enantioselectivity in Au(I)-Catalysis.
Chemistry. 2025 Jun 23;31(35):e202501259. doi: 10.1002/chem.202501259. Epub 2025 May 27.
2
A laterally-fused N-heterocyclic carbene framework from polysubstituted aminoimidazo[5,1-]oxazol-6-ium salts.
Beilstein J Org Chem. 2024 Mar 18;20:621-627. doi: 10.3762/bjoc.20.54. eCollection 2024.
3
Boosting Gold(I) Catalysis via Weak Interactions: New Fine-Tunable Impy Ligands.
ACS Org Inorg Au. 2022 Jan 13;2(3):229-235. doi: 10.1021/acsorginorgau.1c00052. eCollection 2022 Jun 1.
4
New-Generation Ligand Design for the Gold-Catalyzed Asymmetric Activation of Alkynes.
Chempluschem. 2021 Sep;86(9):1283-1296. doi: 10.1002/cplu.202100232.
5
Chiral Bifunctional Phosphine Ligand-Enabled Cooperative Cu Catalysis: Formation of Chiral α,β-Butenolides via Highly Enantioselective γ-Protonation.
J Am Chem Soc. 2021 Jul 28;143(29):10876-10881. doi: 10.1021/jacs.1c05781. Epub 2021 Jul 15.
6
Enantioselective Alkoxycyclization of 1,6-Enynes with Gold(I)-Cavitands: Total Synthesis of Mafaicheenamine C.
Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9339-9344. doi: 10.1002/anie.202017035. Epub 2021 Mar 11.
7
Gold-Catalyzed Synthesis of Small Rings.
Chem Rev. 2021 Jul 28;121(14):8613-8684. doi: 10.1021/acs.chemrev.0c00697. Epub 2020 Nov 2.
本文引用的文献
1
An Original L-shape, Tunable N-Heterocyclic Carbene Platform for Efficient Gold(I) Catalysis.
Angew Chem Int Ed Engl. 2019 Jun 11;58(24):7977-7981. doi: 10.1002/anie.201901090. Epub 2019 May 8.
2
Chiral Bifunctional Phosphine Ligand Enabling Gold-Catalyzed Asymmetric Isomerization of Alkyne to Allene and Asymmetric Synthesis of 2,5-Dihydrofuran.
J Am Chem Soc. 2019 Mar 6;141(9):3787-3791. doi: 10.1021/jacs.8b12833. Epub 2019 Feb 21.
3
Bifunctional Biphenyl-2-ylphosphine Ligand Enables Tandem Gold-Catalyzed Propargylation of Aldehyde and Unexpected Cycloisomerization.
J Am Chem Soc. 2018 Dec 19;140(50):17439-17443. doi: 10.1021/jacs.8b12478. Epub 2018 Dec 10.
4
Bifunctional Ligand Enables Efficient Gold-Catalyzed Hydroalkenylation of Propargylic Alcohol.
Angew Chem Int Ed Engl. 2018 Jul 2;57(27):8250-8254. doi: 10.1002/anie.201802533. Epub 2018 Jun 4.
5
Remote Cooperative Group Strategy Enables Ligands for Accelerative Asymmetric Gold Catalysis.
J Am Chem Soc. 2017 Nov 15;139(45):16064-16067. doi: 10.1021/jacs.7b09136. Epub 2017 Nov 7.
6
Designed Bifunctional Phosphine Ligand-Enabled Gold-Catalyzed Isomerizations of Ynamides and Allenamides: Stereoselective and Regioselective Formation of 1-Amido-1,3-dienes.
Org Lett. 2017 Nov 3;19(21):5744-5747. doi: 10.1021/acs.orglett.7b02624.
7
Enantioselective Synthesis of Cyclobutenes by Intermolecular [2+2] Cycloaddition with Non-C Symmetric Digold Catalysts.
J Am Chem Soc. 2017 Oct 4;139(39):13628-13631. doi: 10.1021/jacs.7b07651. Epub 2017 Sep 22.
8
Ligand-Accelerated Gold-Catalyzed Addition of in Situ Generated Hydrazoic Acid to Alkynes under Neat Conditions.
Org Lett. 2017 Jul 21;19(14):3687-3690. doi: 10.1021/acs.orglett.7b01359. Epub 2017 Jul 11.
9
Gold-Catalyzed Enantioselective Annulations.
Chemistry. 2017 Jan 12;23(3):467-512. doi: 10.1002/chem.201602822. Epub 2016 Oct 10.
10
Recent advances in enantioselective gold catalysis.
Chem Soc Rev. 2016 Aug 8;45(16):4567-89. doi: 10.1039/c5cs00929d.
Zotero 插件