光氧化还原/镍催化单电子 Tsuji-Trost 反应：发展与机理洞察。
Photoredox/Nickel-Catalyzed Single-Electron Tsuji-Trost Reaction: Development and Mechanistic Insights.
机构信息
Department of Chemistry, University of Pennsylvania, Roy and Diana Vagelos Laboratories, Philadelphia, PA, 19104-6323, USA.
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, 20742, USA.
出版信息
Angew Chem Int Ed Engl. 2018 Nov 26;57(48):15847-15851. doi: 10.1002/anie.201809919. Epub 2018 Nov 7.
Abstract
A regioselective, nickel-catalyzed photoredox allylation of secondary, benzyl, and α-alkoxy radical precursors is disclosed. Through this manifold, a variety of linear allylic alcohols and allylated monosaccharides are accessible in high yields under mild reaction conditions. Quantum mechanical calculations [DFT and DLPNO-CCSD(T)] support the mechanistic hypothesis of a Ni to Ni oxidative addition pathway followed by radical addition and inner-sphere allylation.
摘要
本文报道了一种区域选择性、镍催化的次级、苄基和α-烷氧基自由基前体的光还原烯丙基化反应。通过这种多相反应，可以在温和的反应条件下以高产率获得各种线性烯丙基醇和烯丙基单糖。量子力学计算[DFT 和 DLPNO-CCSD(T)]支持 Ni 到 Ni 氧化加成途径，然后是自由基加成和内球烯丙基化的反应机理假设。
相似文献
1
Photoredox/Nickel-Catalyzed Single-Electron Tsuji-Trost Reaction: Development and Mechanistic Insights.光氧化还原/镍催化单电子 Tsuji-Trost 反应：发展与机理洞察。
Angew Chem Int Ed Engl. 2018 Nov 26;57(48):15847-15851. doi: 10.1002/anie.201809919. Epub 2018 Nov 7.
2
Regioselective Single-Electron Tsuji-Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach.区域选择性单电子 Tsuji-Trost 反应的烯丙醇：一种光氧化还原/镍双催化方法。
Org Lett. 2019 Aug 16;21(16):6543-6547. doi: 10.1021/acs.orglett.9b02473. Epub 2019 Aug 7.
3
Single-Electron Transmetalation via Photoredox/Nickel Dual Catalysis: Unlocking a New Paradigm for sp(3)-sp(2) Cross-Coupling.单电子转移的光氧化还原/镍双催化：为 sp(3)-sp(2)交叉偶联开辟新范式。
Acc Chem Res. 2016 Jul 19;49(7):1429-39. doi: 10.1021/acs.accounts.6b00214. Epub 2016 Jul 5.
4
Synthetic and Mechanistic Implications of Chlorine Photoelimination in Nickel/Photoredox C(sp)-H Cross-Coupling.镍/光氧化还原 C(sp)-H 交叉偶联中氯光消除的合成和机理意义。
Acc Chem Res. 2021 Feb 16;54(4):988-1000. doi: 10.1021/acs.accounts.0c00694. Epub 2021 Jan 29.
5
Nickel-catalyzed cross-coupling of photoredox-generated radicals: uncovering a general manifold for stereoconvergence in nickel-catalyzed cross-couplings.镍催化的光氧化还原产生的自由基交叉偶联：揭示镍催化交叉偶联中立体收敛的一般机理。
J Am Chem Soc. 2015 Apr 22;137(15):4896-9. doi: 10.1021/ja513079r. Epub 2015 Apr 8.
6
Single-Electron Transmetalation: Protecting-Group-Independent Synthesis of Secondary Benzylic Alcohol Derivatives via Photoredox/Nickel Dual Catalysis.单电子转移金属化反应：通过光氧化还原/镍双催化实现保护基非依赖的二级苄醇衍生物的合成。
Org Lett. 2016 Jun 3;18(11):2572-5. doi: 10.1021/acs.orglett.6b00911. Epub 2016 May 24.
7
Access to macrocyclic endocyclic and exocyclic allylic alcohols by nickel-catalyzed reductive cyclization of ynals.通过镍催化的烯醛还原环化反应合成大环内烯丙醇和外烯丙醇
J Am Chem Soc. 2005 Sep 28;127(38):13156-7. doi: 10.1021/ja054590i.
8
Highly Regioselective Indoline Synthesis under Nickel/Photoredox Dual Catalysis.镍/光氧化还原双催化下的高区域选择性吲哚啉合成
J Am Chem Soc. 2015 Aug 5;137(30):9531-4. doi: 10.1021/jacs.5b05597. Epub 2015 Jul 21.
9
Direct Synthesis of Secondary Benzylic Alcohols Enabled by Photoredox/Ni Dual-Catalyzed Cross-Coupling.光氧化还原/Ni 双催化交叉偶联促进的二级苄醇的直接合成。
J Org Chem. 2017 Dec 15;82(24):13728-13734. doi: 10.1021/acs.joc.7b02589. Epub 2017 Nov 27.
10
Nickel-catalyzed enantioselective alkylative coupling of alkynes and aldehydes: synthesis of chiral allylic alcohols with tetrasubstituted olefins.镍催化的炔烃与醛的对映选择性烷基化偶联反应：合成具有四取代烯烃的手性烯丙醇
J Am Chem Soc. 2008 Oct 29;130(43):14052-3. doi: 10.1021/ja805296k. Epub 2008 Oct 4.
引用本文的文献
1
Carbon-centered radical capture at nickel(II) complexes: Spectroscopic evidence, rates, and selectivity.镍（II）配合物中碳中心自由基的捕获：光谱证据、速率和选择性。
Chem. 2023 May 11;9(5):1295-1308. doi: 10.1016/j.chempr.2023.02.010. Epub 2023 Mar 13.
2
Nickel-Mediated Radical Capture: Evidence for a Concerted Inner-Sphere Mechanism.镍介导的自由基捕获：协同内球机制的证据。
J Am Chem Soc. 2025 Jun 11;147(23):19632-19642. doi: 10.1021/jacs.5c01554. Epub 2025 May 29.
3
Synthesis of C4-Acyl Glycosides by Cross-Ketonization: The Importance of Precise Temperature Control in Photochemistry.通过交叉酮化反应合成C4-酰基糖苷：光化学中精确温度控制的重要性。
Chemistry. 2025 Jun 3;31(31):e202501408. doi: 10.1002/chem.202501408. Epub 2025 Apr 26.
4
Unlocking the reactivity of the C-In bond: alkyl indium reagents as a source of radicals under photocatalytic conditions.解锁碳-铟键的反应活性：烷基铟试剂作为光催化条件下的自由基来源。
Chem Sci. 2025 Feb 24;16(13):5623-5631. doi: 10.1039/d4sc08521c. eCollection 2025 Mar 26.
5
Highly Functional Allyl-Bicyclo[1.1.1]pentane Synthesis by Radical-Initiated Three-Component Stereoselective Allylation.通过自由基引发的三组分立体选择性烯丙基化反应高效合成功能性烯丙基-双环[1.1.1]戊烷
JACS Au. 2025 Feb 11;5(2):913-921. doi: 10.1021/jacsau.4c01129. eCollection 2025 Feb 24.
6
Advances in Computational Methods for Modeling Photocatalytic Reactions: A Review of Recent Developments.光催化反应建模计算方法的进展：近期发展综述
Materials (Basel). 2024 Apr 30;17(9):2119. doi: 10.3390/ma17092119.
7
Transformations of carbohydrate derivatives enabled by photocatalysis and visible light photochemistry.光催化和可见光光化学实现的碳水化合物衍生物的转化
Chem Sci. 2024 Jan 2;15(4):1204-1236. doi: 10.1039/d3sc05400d. eCollection 2024 Jan 24.
8
Mechanisms, Challenges, and Opportunities of Dual Ni/Photoredox-Catalyzed C(sp)-C(sp) Cross-Couplings.双镍/光氧化还原催化的C(sp)-C(sp)交叉偶联反应的机理、挑战与机遇
Wiley Interdiscip Rev Comput Mol Sci. 2022 May-Jun;12(3). doi: 10.1002/wcms.1573. Epub 2021 Sep 21.
9
Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis.金属光氧化还原：光氧化还原与过渡金属催化的融合
Chem Rev. 2022 Jan 26;122(2):1485-1542. doi: 10.1021/acs.chemrev.1c00383. Epub 2021 Nov 18.
10
Pyridylphosphonium salts as alternatives to cyanopyridines in radical-radical coupling reactions.吡啶鏻盐在自由基-自由基偶联反应中作为氰基吡啶的替代物。
Chem Sci. 2021 Jul 2;12(31):10538-10543. doi: 10.1039/d1sc02324a. eCollection 2021 Aug 11.
本文引用的文献
1
Synthesis of Reversed C-Acyl Glycosides through Ni/Photoredox Dual Catalysis.通过镍/光氧化还原双重催化合成反式 C-酰基糖苷。
Angew Chem Int Ed Engl. 2018 May 28;57(22):6610-6613. doi: 10.1002/anie.201800701. Epub 2018 Apr 17.
2
Synthesis of Non-Classical Arylated C-Saccharides through Nickel/Photoredox Dual Catalysis.通过镍/光氧化还原双重催化合成非经典芳基 C-糖。
Angew Chem Int Ed Engl. 2018 May 28;57(22):6614-6618. doi: 10.1002/anie.201802282. Epub 2018 Apr 14.
3
Nickel/Photoredox-Catalyzed Amidation via Alkylsilicates and Isocyanates.镍/光氧化还原催化的通过硅酸烷基酯和异氰酸酯的酰胺化反应
ACS Catal. 2017 Nov 3;7(11):7957-7961. doi: 10.1021/acscatal.7b02795. Epub 2017 Oct 25.
4
Amycolatopsins A-C: antimycobacterial glycosylated polyketide macrolides from the Australian soil Amycolatopsis sp. MST-108494.枝动菌素A-C：从澳大利亚土壤中分离的枝动菌属菌株MST-108494产生的抗分枝杆菌糖基化聚酮类大环内酯化合物。
J Antibiot (Tokyo). 2017 Dec;70(12):1097-1103. doi: 10.1038/ja.2017.119. Epub 2017 Oct 25.
5
Structural characterisation of the capsular polysaccharide expressed by Burkholderia thailandensis strain E555:: wbiI (pKnock-KmR) and assessment of the significance of the 2-O-acetyl group in immune protection.泰国伯克霍尔德菌E555::wbiI（pKnock-KmR）表达的荚膜多糖的结构表征及2-O-乙酰基团在免疫保护中的意义评估
Carbohydr Res. 2017 Nov 27;452:17-24. doi: 10.1016/j.carres.2017.09.011. Epub 2017 Sep 21.
6
Radical-Based C-C Bond-Forming Processes Enabled by the Photoexcitation of 4-Alkyl-1,4-dihydropyridines.基于 4-烷基-1,4-二氢吡啶光激发的自由基 C-C 键形成过程。
Angew Chem Int Ed Engl. 2017 Nov 20;56(47):15039-15043. doi: 10.1002/anie.201709571. Epub 2017 Oct 24.
7
Direct Conversion of Carboxylic Acids to Alkyl Ketones.羧酸直接转化为酮。
Org Lett. 2017 Jul 7;19(13):3612-3615. doi: 10.1021/acs.orglett.7b01588. Epub 2017 Jun 12.
8
Synergistic Visible-Light Photoredox/Nickel-Catalyzed Synthesis of Aliphatic Ketones via N-C Cleavage of Imides.协同可见光照/镍催化通过亚胺 N-C 裂解合成脂肪酮。
Org Lett. 2017 May 5;19(9):2426-2429. doi: 10.1021/acs.orglett.7b00989. Epub 2017 Apr 26.
9
Photoredox-Mediated Routes to Radicals: The Value of Catalytic Radical Generation in Synthetic Methods Development.光氧化还原介导的自由基生成途径：催化自由基生成在合成方法开发中的价值。
ACS Catal. 2017 Apr 7;7(4):2563-2575. doi: 10.1021/acscatal.7b00094. Epub 2017 Mar 14.
10
Synergistic Photoredox/Nickel Coupling of Acyl Chlorides with Secondary Alkyltrifluoroborates: Dialkyl Ketone Synthesis.酰氯与仲烷基三氟硼酸盐的协同光氧化还原/镍偶联反应：二烷基酮的合成。
J Org Chem. 2017 Feb 3;82(3):1856-1863. doi: 10.1021/acs.joc.6b02897. Epub 2017 Jan 17.
Zotero 插件