通过亚砜翁重排反应实现的三氘甲基化。
Trideuteromethylation Enabled by a Sulfoxonium Metathesis Reaction.
机构信息
State Key Laboratory of Bioengineering Reactor, and Shanghai Key Laboratory of New Drug Design, School of Pharmacy , East China University of Science & Technology , Shanghai 200237 , China.
Jiangsu Key Laboratory of Neuropsychiatric Diseases and College of Pharmaceutical Sciences , Soochow University , 199 Ren'ai Road , Suzhou , Jiangsu 215123 , China.
出版信息
Org Lett. 2019 Jan 18;21(2):448-452. doi: 10.1021/acs.orglett.8b03641. Epub 2019 Jan 7.
Abstract
A conceptually novel sulfoxonium metathesis reaction between TMSOI and cost-effective DMSO- d is developed for the efficient generation of a new trideuteromethylation reagent TDMSOI. The new reagent TDMSOI is produced highly efficiently by simply heating a mixture of TMSOI and DMSO- d and directly used for subsequent trideuteromethylation in a "one-pot" operation. The preparative power of the new versatile reagent and the "one-pot" protocol is demonstrated by its use to install the -CD moiety into broad functionalities including phenols, thiophenols, acidic amines, and enolizable methylene units in high yield and at a useful level of deuteration (>87% D).
摘要
开发了一种新颖的 TMSOI 和经济有效的 DMSO- d 之间的亚磺酰亚胺复分解反应，用于高效生成新的三氘甲基化试剂 TDMSOI。通过简单地加热 TMSOI 和 DMSO- d 的混合物并直接用于随后的“一锅”操作中的三氘甲基化，高效地生成了新的试剂 TDMSOI。新的多功能试剂和“一锅”方案的制备能力通过将-CD 部分安装到包括酚，硫酚，酸性胺和烯醇化亚甲基单元在内的广泛官能团中得到证明，收率高，氘化水平高（>87％D）。
相似文献
1
Trideuteromethylation Enabled by a Sulfoxonium Metathesis Reaction.通过亚砜翁重排反应实现的三氘甲基化。
Org Lett. 2019 Jan 18;21(2):448-452. doi: 10.1021/acs.orglett.8b03641. Epub 2019 Jan 7.
2
Reaction of isocyanides with thiophenols and gem-diactivated olefins: a one-pot synthesis of substituted 2-aminopyrroles.异氰化物与噻酚和偕二官能团烯烃的反应：取代 2-氨基吡啶的一锅合成法。
Mol Divers. 2010 Aug;14(3):543-50. doi: 10.1007/s11030-010-9233-x. Epub 2010 Mar 7.
3
An improved procedure for the three-component synthesis of highly substituted pyridines using ionic liquid.一种使用离子液体进行高取代吡啶三组分合成的改进方法。
J Org Chem. 2007 Apr 13;72(8):3152-4. doi: 10.1021/jo070015g. Epub 2007 Mar 17.
4
Role of sulfur compounds in the detection of amino acids by ninhydrin on TLC plate.硫化物在薄层色谱板上茚三酮检测氨基酸中的作用。
J Chromatogr Sci. 2005 Feb;43(2):104-5. doi: 10.1093/chromsci/43.2.104.
5
Facile access to -methyl dithiocarbamates with sulfonium or sulfoxonium iodide as a methylation reagent.以锍盐或碘化亚砜鎓盐作为甲基化试剂，可便捷地制备甲基二硫代氨基甲酸盐。
Org Biomol Chem. 2023 Aug 16;21(32):6474-6478. doi: 10.1039/d3ob00932g.
6
A highly active and magnetically retrievable nanoferrite-DOPA-copper catalyst for the coupling of thiophenols with aryl halides.一种高活性和可磁回收的纳米铁氧体-DOPA-铜催化剂，用于噻吩酚与芳基卤化物的偶联反应。
Chem Commun (Camb). 2012 Mar 7;48(20):2582-4. doi: 10.1039/c2cc17283f. Epub 2012 Jan 31.
7
2-(Diethylamino)ethanethiol, a new reagent for the odorless deprotection of aromatic methyl ethers.2-（二乙氨基）乙硫醇，一种用于芳香族甲基醚无臭脱保护的新型试剂。
J Org Chem. 2006 Sep 1;71(18):7103-5. doi: 10.1021/jo0611059.
8
Oxidative nucleophilic cyclization of 2-alkynylanilines with thiophenols under metal-free conditions.2-炔基苯胺与苯硫酚在无金属条件下的氧化亲核环化反应
Org Lett. 2014 Dec 19;16(24):6508-11. doi: 10.1021/ol5034139. Epub 2014 Dec 11.
9
{7-[Bis(carboxymethyl)amino]coumarin-4-yl}methoxycarbonyl derivatives for photorelease of carboxylic acids, alcohols/phenols, thioalcohols/thiophenols, and amines.用于光释放羧酸、醇/酚、硫醇/硫酚和胺的{7-[双(羧甲基)氨基]香豆素-4-基}甲氧基羰基衍生物。
Chemistry. 2008;14(5):1621-7. doi: 10.1002/chem.200701142.
10
Synthesis of ionic liquid-supported sulfonyl azide and its application in diazotransfer reaction.离子液体支撑的磺酰叠氮的合成及其在重氮转移反应中的应用。
J Org Chem. 2012 Oct 5;77(19):8787-91. doi: 10.1021/jo301529b. Epub 2012 Sep 19.
引用本文的文献
1
Recent advances in synthetic approaches for bioactive cinnamic acid derivatives.生物活性肉桂酸衍生物合成方法的最新进展。
Beilstein J Org Chem. 2025 May 28;21:1031-1086. doi: 10.3762/bjoc.21.85. eCollection 2025.
2
Access to arynes from arenes net dehydrogenation: scope, synthetic applications and mechanistic analysis.通过芳烃的净脱氢反应制备芳炔：范围、合成应用及机理分析。
Chem Sci. 2025 Feb 20;16(13):5547-5558. doi: 10.1039/d5sc00054h. eCollection 2025 Mar 26.
3
Unlocking the potential of hydrogen deuterium exchange via an iterative continuous-flow deuteration process.通过迭代连续流氘化过程释放氢氘交换的潜力。
Nat Commun. 2025 Feb 3;16(1):1314. doi: 10.1038/s41467-025-56600-8.
4
An interrupted Corey-Chaykovsky reaction of designed azaarenium salts: synthesis of complex polycyclic spiro- and fused cyclopropanoids.设计氮杂芳鎓盐的间断式Corey-Chaykovsky反应：复杂多环螺环和稠合环丙烷类化合物的合成
Chem Sci. 2023 Jun 1;14(25):6963-6969. doi: 10.1039/d3sc01578e. eCollection 2023 Jun 28.
5
Recent Advances in the Use of Dimethyl Sulfoxide as a Synthon in Organic Chemistry.二甲基亚砜在有机化学中作为合成子的最新进展。
Top Curr Chem (Cham). 2022 Oct 28;380(6):55. doi: 10.1007/s41061-022-00411-8.
6
Trialkylammonium salt degradation: implications for methylation and cross-coupling.三烷基铵盐降解：对甲基化和交叉偶联的影响。
Chem Sci. 2021 Apr 13;12(20):6949-6963. doi: 10.1039/d1sc00757b.
7
The Deuterated "Magic Methyl" Group: A Guide to Site-Selective Trideuteromethyl Incorporation and Labeling by Using CD Reagents.氘代“神奇甲基”基团：使用 CD 试剂进行选择性三氘甲基化和标记的指南。
Chemistry. 2021 Aug 16;27(46):11751-11772. doi: 10.1002/chem.202101179. Epub 2021 Jul 7.
8
Semiconductor photocatalysis to engineering deuterated N-alkyl pharmaceuticals enabled by synergistic activation of water and alkanols.半导体光催化协同激活水和醇实现工程氘代 N-烷基药物
Nat Commun. 2020 Sep 18;11(1):4722. doi: 10.1038/s41467-020-18458-w.
9
Bioinspired design of a robust -methylating agent.一种强大的甲基化试剂的仿生设计。
Sci Adv. 2020 May 8;6(19):eaba0946. doi: 10.1126/sciadv.aba0946. eCollection 2020 May.
10
Synthesis of Enantioenriched α-Deuterated α-Amino Acids Enabled by an Organophotocatalytic Radical Approach.通过有机光催化自由基方法合成对映体富集的α-氘代α-氨基酸。
Org Lett. 2020 Feb 21;22(4):1557-1562. doi: 10.1021/acs.orglett.0c00154. Epub 2020 Feb 11.
本文引用的文献
1
Deoxygenative Deuteration of Carboxylic Acids with D O.用 DO 对羧酸进行脱氧氘代。
Angew Chem Int Ed Engl. 2019 Jan 2;58(1):312-316. doi: 10.1002/anie.201811522. Epub 2018 Nov 16.
2
Catalytic Isofunctional Reactions-Expanding the Repertoire of Shuttle and Metathesis Reactions.催化同功能反应——拓展穿梭和复分解反应的应用范围。
Angew Chem Int Ed Engl. 2019 Jul 22;58(30):10074-10103. doi: 10.1002/anie.201803797. Epub 2019 Apr 30.
3
Reductive Deuteration of Nitriles: The Synthesis of α,α-Dideuterio Amines by Sodium-Mediated Electron Transfer Reactions.腈的还原氘代反应：通过钠介导的电子转移反应合成α,α-二氘代胺。
J Org Chem. 2018 Oct 5;83(19):12269-12274. doi: 10.1021/acs.joc.8b01730. Epub 2018 Aug 27.
4
General and Practical Potassium Methoxide/Disilane-Mediated Dehalogenative Deuteration of (Hetero)Arylhalides.通用且实用的甲醇钾/乙硅烷介导的（杂）芳基卤化物脱卤氘代反应
J Am Chem Soc. 2018 Sep 5;140(35):10970-10974. doi: 10.1021/jacs.8b07597. Epub 2018 Aug 22.
5
Palladium-Catalyzed H/D Exchange Reaction with 8-Aminoquinoline as the Directing Group: Access to ortho-Selective Deuterated Aromatic Acids and β-Selective Deuterated Aliphatic Acids.以8-氨基喹啉为导向基团的钯催化氢/氘交换反应：合成邻位选择性氘代芳香酸和β-选择性氘代脂肪族酸。
J Org Chem. 2018 Aug 3;83(15):7860-7866. doi: 10.1021/acs.joc.8b00734. Epub 2018 Jul 12.
6
Highly Selective Directed Iridium-Catalyzed Hydrogen Isotope Exchange Reactions of Aliphatic Amides.脂肪族酰胺的高选择性定向铱催化氢同位素交换反应
Angew Chem Int Ed Engl. 2018 Jul 2;57(27):8159-8163. doi: 10.1002/anie.201804010. Epub 2018 May 30.
7
Photocatalytic Deuteration of Halides Using D O over CdSe Porous Nanosheets: A Mild and Controllable Route to Deuterated Molecules.利用氧化氘在CdSe多孔纳米片上对卤化物进行光催化氘代：一种制备氘代分子的温和且可控的途径。
Angew Chem Int Ed Engl. 2018 May 14;57(20):5590-5592. doi: 10.1002/anie.201801541. Epub 2018 Apr 6.
8
Palladium-Catalyzed Regioselective C-H Functionalization of Arenes Substituted by Two N-Heterocycles and Application in Late-Stage Functionalization.钯催化的含有两个杂环取代的芳烃的区域选择性 C-H 功能化及其在晚期功能化中的应用。
J Org Chem. 2018 Apr 6;83(7):3987-4001. doi: 10.1021/acs.joc.8b00322. Epub 2018 Mar 15.
9
One-Pot Synthesis of Deuterated Aldehydes from Arylmethyl Halides.一锅法从芳基卤代烃制备氘代醛。
Org Lett. 2018 Apr 6;20(7):1712-1715. doi: 10.1021/acs.orglett.8b00016. Epub 2018 Mar 8.
10
Ruthenium-catalyzed hydrogen isotope exchange of C(sp)-H bonds directed by a sulfur atom.硫原子导向的钌催化C(sp)-H键的氢同位素交换反应
Chem Commun (Camb). 2018 Mar 25;54(24):2986-2989. doi: 10.1039/c8cc00653a. Epub 2018 Mar 5.
Zotero 插件