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。
Direct Synthesis of Secondary Benzylic Alcohols Enabled by Photoredox/Ni Dual-Catalyzed Cross-Coupling.
机构信息
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, United States.
出版信息
J Org Chem. 2017 Dec 15;82(24):13728-13734. doi: 10.1021/acs.joc.7b02589. Epub 2017 Nov 27.
Abstract
An operationally simple, mild, redox-neutral method for the cross-coupling of α-hydroxyalkyltrifluoroborates is reported. Utilizing an Ir photocatalyst, α-hydroxyalkyl radicals are generated from the single-electron oxidation of the trifluoroborates, and these radicals are subsequently engaged in a nickel-catalyzed C-C bond-forming reaction with aryl halides. The process is highly selective, functional group tolerant, and step economical, which allows the direct synthesis of secondary benzylic alcohol motifs.
摘要
报告了一种操作简单、温和、氧化还原中性的α-羟基烷基三氟硼酸盐交叉偶联方法。利用 Ir 光催化剂，通过三氟硼酸盐的单电子氧化生成α-羟基烷基自由基，然后这些自由基与芳基卤化物进行镍催化的 C-C 键形成反应。该过程具有高度选择性、官能团耐受性和经济性，可直接合成仲苄醇基序。
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2
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J Am Chem Soc. 2017 Jul 26;139(29):9847-9850. doi: 10.1021/jacs.7b06288. Epub 2017 Jul 18.
3
Visible-Light-Triggered Directly Reductive Arylation of Carbonyl/Iminyl Derivatives through Photocatalytic PCET.
Org Lett. 2017 Jul 21;19(14):3807-3810. doi: 10.1021/acs.orglett.7b01677. Epub 2017 Jul 11.
4
Site-selective carbon-carbon bond formation in unprotected monosaccharides using photoredox catalysis.
Chem Commun (Camb). 2017 May 2;53(36):4926-4929. doi: 10.1039/c7cc01416c.
5
Photoredox-Mediated Routes to Radicals: The Value of Catalytic Radical Generation in Synthetic Methods Development.
ACS Catal. 2017 Apr 7;7(4):2563-2575. doi: 10.1021/acscatal.7b00094. Epub 2017 Mar 14.
6
Preparation of visible-light-activated metal complexes and their use in photoredox/nickel dual catalysis.
Nat Protoc. 2017 Mar;12(3):472-492. doi: 10.1038/nprot.2016.176. Epub 2017 Feb 2.
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10
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