手性双氮配体对芳环 C-H 键的对映选择性硼化反应。
Enantioselective Borylation of Aromatic C-H Bonds with Chiral Dinitrogen Ligands.
机构信息
Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry and Molecular Engineering, Peking University, Beijing, China.
Department of Chemistry, University of California, Berkeley, CA, 94720, USA.
出版信息
Angew Chem Int Ed Engl. 2017 Jun 12;56(25):7205-7208. doi: 10.1002/anie.201702628. Epub 2017 May 16.
Abstract
The borylation of C-H bonds catalyzed by transition metals has been investigated extensively in the past two decades, but no iridium-catalyzed enantioselective borylation of C-H bonds has been reported. We report a set of iridium-catalyzed enantioselective borylations of aromatic C-H bonds. This reaction relies on a set of newly developed chiral quinolyl oxazoline ligands. This process proceeds under mild conditions with good to excellent enantioselectivity, and the borylated products can be converted to enantioenriched derivatives containing new C-O, C-C, C-Cl, or C-Br bonds.
摘要
在过去的二十年中，过渡金属催化的 C-H 键硼化反应得到了广泛的研究，但尚未有报道过铱催化的 C-H 键对映选择性硼化反应。我们报告了一组铱催化的芳香族 C-H 键对映选择性硼化反应。该反应依赖于一组新开发的手性喹啉恶唑啉配体。该过程在温和的条件下进行，具有良好到优异的对映选择性，并且硼化产物可以转化为含有新的 C-O、C-C、C-Cl 或 C-Br 键的对映体富集衍生物。
相似文献
1
Enantioselective Borylation of Aromatic C-H Bonds with Chiral Dinitrogen Ligands.手性双氮配体对芳环 C-H 键的对映选择性硼化反应。
Angew Chem Int Ed Engl. 2017 Jun 12;56(25):7205-7208. doi: 10.1002/anie.201702628. Epub 2017 May 16.
2
A Chiral Nitrogen Ligand for Enantioselective, Iridium-Catalyzed Silylation of Aromatic C-H Bonds.手性氮配体用于对映选择性的铱催化芳基 C-H 键硅氢化反应。
Angew Chem Int Ed Engl. 2017 Jan 19;56(4):1092-1096. doi: 10.1002/anie.201609939. Epub 2016 Dec 15.
3
Development of Chiral Ligands for the Transition-Metal-Catalyzed Enantioselective Silylation and Borylation of C-H Bonds.发展过渡金属催化的 C-H 键手性硅化和硼化反应中的手性配体。
Angew Chem Int Ed Engl. 2022 Feb 21;61(9):e202113343. doi: 10.1002/anie.202113343. Epub 2021 Dec 21.
4
Iridium-catalyzed C-H borylation of heteroarenes: scope, regioselectivity, application to late-stage functionalization, and mechanism.铱催化杂芳烃的 C-H 硼化反应：范围、区域选择性、在晚期官能化中的应用及机理。
J Am Chem Soc. 2014 Mar 19;136(11):4287-99. doi: 10.1021/ja412563e. Epub 2014 Mar 6.
5
Ir-Catalyzed Enantioselective, Intramolecular Silylation of Methyl C-H Bonds.铱催化的对映选择性、甲基 C-H 键的分子内硅氢化反应。
J Am Chem Soc. 2017 Sep 6;139(35):12137-12140. doi: 10.1021/jacs.7b06679. Epub 2017 Aug 25.
6
Iridium-Catalyzed Enantioselective C(sp )-H Borylation of Aminocyclopropanes.铱催化的氨基环丙烷的对映选择性C(sp )-H硼化反应
Angew Chem Int Ed Engl. 2022 May 2;61(19):e202201463. doi: 10.1002/anie.202201463. Epub 2022 Mar 14.
7
para-C-H Borylation of Benzene Derivatives by a Bulky Iridium Catalyst.用大位阻的铱催化剂实现苯衍生物的 para-C-H 硼化反应。
J Am Chem Soc. 2015 Apr 22;137(15):5193-8. doi: 10.1021/jacs.5b02052. Epub 2015 Apr 10.
8
Enantioselective total syntheses of (-)-taiwaniaquinone H and (-)-taiwaniaquinol B by iridium-catalyzed borylation and palladium-catalyzed asymmetric α-arylation.通过铱催化的硼化和钯催化的不对称 α-芳基化反应，对（-）-taiwaniaquinone H 和（-）-taiwaniaquinol B 进行对映选择性全合成。
J Am Chem Soc. 2011 Feb 23;133(7):2088-91. doi: 10.1021/ja110215b. Epub 2011 Jan 26.
9
Iridium-catalyzed C-H activation versus directed ortho metalation: complementary borylation of aromatics and heteroaromatics.铱催化的 C-H 活化与导向邻位金属化：芳烃和杂芳烃的互补硼化反应。
Chemistry. 2010 Jul 19;16(27):8155-61. doi: 10.1002/chem.201000401.
10
Highly regio- and enantioselective catalytic asymmetric hydroboration of α-substituted styrenyl derivatives.高区域和对映选择性催化不对称氢化α-取代苯乙烯衍生物。
Chem Commun (Camb). 2011 Jan 7;47(1):298-300. doi: 10.1039/c0cc01547d. Epub 2010 Oct 14.
引用本文的文献
1
Development of Chiral Ligands for the Transition-Metal-Catalyzed Enantioselective Silylation and Borylation of C-H Bonds.发展过渡金属催化的 C-H 键手性硅化和硼化反应中的手性配体。
Angew Chem Int Ed Engl. 2022 Feb 21;61(9):e202113343. doi: 10.1002/anie.202113343. Epub 2021 Dec 21.
2
Asymmetric Catalysis Mediated by Synthetic Peptides, Version 2.0: Expansion of Scope and Mechanisms.由合成肽介导的不对称催化，版本 2.0：范围和机制的扩展。
Chem Rev. 2020 Oct 28;120(20):11479-11615. doi: 10.1021/acs.chemrev.0c00523. Epub 2020 Sep 24.
3
Iridium-Catalyzed Silylation of Unactivated C-H Bonds.铱催化未活化碳氢键的硅基化反应
Tetrahedron. 2019 Aug 2;75(31):4059-4070. doi: 10.1016/j.tet.2019.05.055. Epub 2019 May 27.
4
Hydrogen Bond Directed ortho-Selective C-H Borylation of Secondary Aromatic Amides.氢键导向的仲芳酰胺邻位选择性C-H硼化反应
Angew Chem Int Ed Engl. 2019 Sep 9;58(37):13039-13043. doi: 10.1002/anie.201907366. Epub 2019 Jul 17.
5
A comprehensive overview of directing groups applied in metal-catalysed C-H functionalisation chemistry.指导基团在金属催化 C-H 官能化化学中的应用综述。
Chem Soc Rev. 2018 Aug 28;47(17):6603-6743. doi: 10.1039/c8cs00201k.
6
Iridium-Catalyzed, Silyl-Directed, peri-Borylation of C-H Bonds in Fused Polycyclic Arenes and Heteroarenes.铱催化的、硅基导向的稠合多环芳烃和杂芳烃中C-H键的邻位硼化反应
Angew Chem Int Ed Engl. 2018 Aug 6;57(32):10163-10167. doi: 10.1002/anie.201805086. Epub 2018 Jul 13.
7
Enantioselective C(sp)‒H bond activation by chiral transition metal catalysts.手性过渡金属催化剂催化的对映选择性C(sp)‒H键活化
Science. 2018 Feb 16;359(6377). doi: 10.1126/science.aao4798.
8
Desymmetrization of Diarylmethylamido Bis(phenols) through Peptide-Catalyzed Bromination: Enantiodivergence as a Consequence of a 2 amu Alteration at an Achiral Residue within the Catalyst.手性酰胺双酚的肽催化溴化去对称化：非手性残基上 2 amu 的变化导致对映体发散。
J Org Chem. 2017 Nov 3;82(21):11326-11336. doi: 10.1021/acs.joc.7b02339.
本文引用的文献
1
Formation of Aryl- and Benzylboronate Esters by Rhodium-Catalyzed C-H Bond Functionalization with Pinacolborane.通过铑催化的碳氢键与频哪醇硼烷的官能团化反应形成芳基硼酸酯和苄基硼酸酯。
Angew Chem Int Ed Engl. 2001 Jun 1;40(11):2168-2171. doi: 10.1002/1521-3773(20010601)40:11<2168::AID-ANIE2168>3.0.CO;2-0.
2
Pd(II)-Catalyzed Enantioselective C(sp)-H Borylation.钯（II）催化的对映选择性 C(sp)-H 硼化反应。
J Am Chem Soc. 2017 Mar 8;139(9):3344-3347. doi: 10.1021/jacs.6b13389. Epub 2017 Feb 23.
3
N,B-Bidentate Boryl Ligand-Supported Iridium Catalyst for Efficient Functional-Group-Directed C-H Borylation.N,B-双齿硼基配体负载铱催化剂用于高效功能基团导向的 C-H 硼化反应。
J Am Chem Soc. 2017 Jan 11;139(1):91-94. doi: 10.1021/jacs.6b11867. Epub 2016 Dec 21.
4
Construction of Chiral Tetraorganosilicons by Tandem Desymmetrization of Silacyclobutanes/Intermolecular Dehydrogenative Silylation.通过硅杂环丁烷的串联去对称化/分子间脱氢硅氢化反应构建手性四有机硅
Angew Chem Int Ed Engl. 2017 Jan 19;56(4):1125-1129. doi: 10.1002/anie.201609022. Epub 2016 Dec 19.
5
A Chiral Nitrogen Ligand for Enantioselective, Iridium-Catalyzed Silylation of Aromatic C-H Bonds.手性氮配体用于对映选择性的铱催化芳基 C-H 键硅氢化反应。
Angew Chem Int Ed Engl. 2017 Jan 19;56(4):1092-1096. doi: 10.1002/anie.201609939. Epub 2016 Dec 15.
6
Rhodium(III)-Catalyzed Enantiotopic C-H Activation Enables Access to P-Chiral Cyclic Phosphinamides.铑(III)催化的对映选择性 C-H 活化可获得 P-手性环状磷酰胺。
Angew Chem Int Ed Engl. 2017 Jan 2;56(1):364-367. doi: 10.1002/anie.201606637. Epub 2016 Aug 30.
7
High-Turnover Aromatic C-H Borylation Catalyzed by POCOP-Type Pincer Complexes of Iridium.高转化率芳香 C-H 硼化反应由 POCOP 型铱钳形配合物催化。
J Am Chem Soc. 2016 Aug 3;138(30):9487-97. doi: 10.1021/jacs.6b03656. Epub 2016 Jul 20.
8
Rhodium-Catalyzed Enantioselective Silylation of Cyclopropyl C-H Bonds.铑催化的环丙基 C-H 键的对映选择性硅氢化反应。
Angew Chem Int Ed Engl. 2016 Jul 18;55(30):8723-7. doi: 10.1002/anie.201603153. Epub 2016 Jun 2.
9
Iridium-Catalyzed, Hydrosilyl-Directed Borylation of Unactivated Alkyl C-H Bonds.铱催化、氢硅基导向的未活化烷基C-H键的硼化反应
J Am Chem Soc. 2016 Jan 27;138(3):762-5. doi: 10.1021/jacs.5b12153. Epub 2016 Jan 15.
10
Formal Ir-Catalyzed Ligand-Enabled Ortho and Meta Borylation of Aromatic Aldehydes via in Situ-Generated Imines.通过原位生成的亚胺，Ir 催化的配体促进的芳基醛的邻位和间位硼化。
J Am Chem Soc. 2016 Jan 13;138(1):84-7. doi: 10.1021/jacs.5b11683. Epub 2015 Dec 28.
Zotero 插件