使用溴化钠和Selectfluor对醇、醛和二醇进行氧化反应
Oxidations of Alcohols, Aldehydes, and Diols Using NaBr and Selectfluor.
作者信息
Joshi Harshit, Paul Debobrata, Sathyamoorthi Shyam
机构信息
Department of Medicinal Chemistry, University of Kansas, Lawrence, Kansas 66047, United States.
出版信息
J Org Chem. 2023 Aug 4;88(15):11240-11252. doi: 10.1021/acs.joc.3c01307. Epub 2023 Jul 25.
Abstract
We present protocols for the oxidation of alcohols and aldehydes and for the oxidative cyclization of diols which use a combination of Selectfluor and NaBr. For most substrates, the optimal solvent system is a 1:1 mixture of CHCN/HO, but, in select cases, biphasic 1:1 mixtures of EtOAc/HO or CHCl/HO are superior. This procedure is operationally simple, uses inexpensive and readily available reagents, and tolerates a variety of functional groups. Mechanistic studies suggest that the active oxidant is hypobromous acid, generated by the almost instantaneous oxidation of Br by Selectfluor in an aqueous milieu.
摘要
我们展示了使用Selectfluor和NaBr组合对醇和醛进行氧化以及对二醇进行氧化环化的方案。对于大多数底物，最佳溶剂体系是CHCN/H₂O的1:1混合物，但在某些情况下，EtOAc/H₂O或CHCl₃/H₂O的双相1:1混合物更优。该方法操作简单，使用廉价且易于获得的试剂，并且能耐受多种官能团。机理研究表明，活性氧化剂是次溴酸，它是由Selectfluor在水介质中几乎瞬间氧化Br⁻生成的。
相似文献
1
Oxidations of Alcohols, Aldehydes, and Diols Using NaBr and Selectfluor.使用溴化钠和Selectfluor对醇、醛和二醇进行氧化反应
J Org Chem. 2023 Aug 4;88(15):11240-11252. doi: 10.1021/acs.joc.3c01307. Epub 2023 Jul 25.
2
Synthetic applications of nonmetal catalysts for homogeneous oxidations.用于均相氧化的非金属催化剂的合成应用。
Chem Rev. 2001 Nov;101(11):3499-548. doi: 10.1021/cr000019k.
3
Asymmetric fluorocyclizations of alkenes.不对称氟环化反应。
Acc Chem Res. 2014 Dec 16;47(12):3560-70. doi: 10.1021/ar500282z. Epub 2014 Nov 7.
4
Retropinacol/cross-pinacol coupling reactions--a catalytic access to 1,2-unsymmetrical diols.频哪醇重排/交叉频哪醇偶联反应——一种催化制备1,2-不对称二醇的方法。
J Vis Exp. 2014 Apr 4(86):51258. doi: 10.3791/51258.
5
Efficient and Highly Selective Oxidation of Primary Alcohols to Aldehydes by N-Chlorosuccinimide Mediated by Oxoammonium Salts.通过氧鎓盐介导的N-氯代琥珀酰亚胺将伯醇高效且高度选择性地氧化为醛
J Org Chem. 1996 Oct 18;61(21):7452-7454. doi: 10.1021/jo9609790.
6
TEMPO/HCl/NaNO2 catalyst: a transition-metal-free approach to efficient aerobic oxidation of alcohols to aldehydes and ketones under mild conditions.TEMPO/HCl/NaNO₂催化剂：一种在温和条件下将醇高效有氧氧化为醛和酮的无过渡金属方法。
Chemistry. 2008;14(9):2679-85. doi: 10.1002/chem.200701818.
7
Visible-light promoted oxidative cyclization of cinnamic acid derivatives using xanthone as the photocatalyst.可见光促进黄烷酮作为光催化剂的肉桂酸衍生物的氧化环化。
Org Biomol Chem. 2021 Jan 28;19(3):568-573. doi: 10.1039/d0ob02417a.
8
Nickel-Catalyzed Decarboxylative Coupling of Redox-Active Esters with Aliphatic Aldehydes.镍催化的氧化还原活性酯与脂肪醛的脱羧偶联反应。
J Am Chem Soc. 2021 Dec 22;143(50):21234-21240. doi: 10.1021/jacs.1c11170. Epub 2021 Dec 13.
9
Organo-photocatalytic C-H bond oxidation: an operationally simple and scalable method to prepare ketones with ambient air.有机光催化碳氢键氧化：一种操作简单且可扩展的利用环境空气制备酮的方法。
RSC Adv. 2023 Mar 6;13(11):7168-7178. doi: 10.1039/d3ra00332a. eCollection 2023 Mar 1.
10
Copper(I)/TEMPO-catalyzed aerobic oxidation of primary alcohols to aldehydes with ambient air.铜（I）/TEMPO 催化的伯醇在空气中的有氧氧化为醛。
Nat Protoc. 2012 May 24;7(6):1161-6. doi: 10.1038/nprot.2012.057.
引用本文的文献
1
Transformation of Linear Alkenyl -Alkoxy Carbamates into Cyclic Bromo Carbonates.线性链烯基-烷氧基氨基甲酸酯向环状溴代碳酸酯的转化
Chemistry (Basel). 2025 Jun;7(3). doi: 10.3390/chemistry7030099. Epub 2025 Jun 16.
2
Harnessing tethered nitreniums for diastereoselective amino-sulfonoxylation of alkenes.利用 tethered 氮宾实现烯烃的非对映选择性氨磺酰氧基化反应。
Beilstein J Org Chem. 2025 May 19;21:947-954. doi: 10.3762/bjoc.21.78. eCollection 2025.
3
Large-Scale NaBr/Selectfluor Mediated Alcohol Oxidation: Conversion of (-)-Borneol into (-)-Camphor.大规模溴化钠/Selectfluor介导的醇氧化反应：（-）-冰片醇转化为（-）-樟脑
Organic Synth. 2025;102:100-113. doi: 10.15227/orgsyn.102.0100. Epub 2025 Feb 28.
4
Intramolecular Silanoxy-Michael Reactions with Pendant Nitroalkenes: Racemic and Enantioselective.与侧链硝基烯烃的分子内硅烷氧基-迈克尔反应：外消旋和对映选择性反应
J Org Chem. 2024 Oct 4;89(19):14197-14203. doi: 10.1021/acs.joc.4c01625. Epub 2024 Sep 21.
本文引用的文献
1
Palladium-catalyzed C(sp)-H nitrooxylation of masked alcohols.钯催化的掩蔽醇的 C(sp 3 )-H 硝基氧化反应。
Org Biomol Chem. 2022 Dec 21;21(1):75-79. doi: 10.1039/d2ob01919a.
2
Selectfluor and TBAX (Cl, Br) Mediated Oxidative Chlorination and Bromination of Olefins.Selectfluor和四丁基铵卤化物（氯、溴）介导的烯烃氧化氯化和溴化反应
Org Lett. 2022 Nov 18;24(45):8261-8264. doi: 10.1021/acs.orglett.2c02627. Epub 2022 Sep 21.
3
Radical C(sp3)-H functionalization and cross-coupling reactions.自由基C(sp3)-H官能团化及交叉偶联反应
Nat Rev Chem. 2022 Jun;6(6):405-427. doi: 10.1038/s41570-022-00388-4. Epub 2022 May 17.
4
Benzylic Fluorination Induced by a Charge-Transfer Complex with a Solvent-Dependent Selectivity Switch.由电荷转移络合物引发的苄基氟化反应，具有溶剂依赖性选择性开关。
Org Lett. 2022 Jul 29;24(29):5376-5380. doi: 10.1021/acs.orglett.2c02050. Epub 2022 Jul 17.
5
γ C-H Functionalization of Amines via Triple H-Atom Transfer of a Vinyl Sulfonyl Radical Chaperone.γ 位胺的 C-H 官能团化：通过乙烯砜基自由基辅助的三重 H 原子转移。
J Am Chem Soc. 2022 Jul 27;144(29):13366-13373. doi: 10.1021/jacs.2c05266. Epub 2022 Jul 12.
6
Reinvestigating FeBr-Catalyzed Alcohol Oxidation with HO: Is a High-Valent Iron Species (HIS) or a Reactive Brominating Species (RBS) Responsible for Alcohol Oxidation?用HO重新研究FeBr催化的醇氧化反应：醇氧化反应的原因是高价铁物种（HIS）还是活性溴化物种（RBS）？
Org Lett. 2022 May 20;24(19):3499-3503. doi: 10.1021/acs.orglett.2c01133. Epub 2022 May 6.
7
A general strategy for C(sp)-H functionalization with nucleophiles using methyl radical as a hydrogen atom abstractor.使用甲基自由基作为氢原子抽离剂的 C(sp)-H 官能团化的一般策略。
Nat Commun. 2021 Nov 29;12(1):6950. doi: 10.1038/s41467-021-27165-z.
8
Photoredox-Catalyzed C-H Functionalization Reactions.光氧化还原催化的 C-H 功能化反应。
Chem Rev. 2022 Jan 26;122(2):1925-2016. doi: 10.1021/acs.chemrev.1c00311. Epub 2021 Sep 29.
9
Oxidation of Primary Alcohols and Aldehydes to Carboxylic Acids via Hydrogen Atom Transfer.通过氢原子转移将伯醇和醛氧化为羧酸。
Org Lett. 2021 Sep 3;23(17):6648-6653. doi: 10.1021/acs.orglett.1c02188. Epub 2021 Aug 16.
10
Selectfluor-Enabled C(sp)-H Alkoxylation of 3-Methylfuranocoumarins.利用 Selectfluor 实现 3-甲基香豆素的 C(sp3)-H 烷氧基化反应。
J Org Chem. 2021 Jun 4;86(11):7864-7871. doi: 10.1021/acs.joc.1c00776. Epub 2021 May 25.
Zotero 插件