Selective cross-dehydrogenative C-O coupling of N-hydroxy compounds with pyrazolones. Introduction of the diacetyliminoxyl radical into the practice of organic synthesis

被引：41

作者：

Krylov, Igor B. ^{[1
]}

Paveliev, Stanislav A. ^{[1
]}

Shelimov, Boris N. ^{[1
]}

Lokshin, Boris V. ^{[2
]}

Garbuzova, Irina A. ^{[2
]}

Tafeenko, Viktor A. ^{[3
]}

Chernyshev, Vladimir V. ^{[3
,4
]}

Budnikov, Alexander S. ^{[1
,5
]}

Nikishin, Gennady I. ^{[1
]}

Terent'ev, Alexander O. ^{[1
]}

机构：

[1] Russian Acad Sci, ND Zelinsky Inst Organ Chem, 47 Leninsky Prosp, Moscow 119991, Russia

[2] Russian Acad Sci, AN Nesmeyanov Inst Organoelement Cpds, 28 Vavilova St, Moscow 119991, Russia

[3] Moscow MV Lomonosov State Univ, Dept Chem, 1-3 Leninskie Gory, Moscow 119991, Russia

[4] RAS, AN Frumkin Inst Phys Chem & Electrochem, 31 Leninsky Prospect, Moscow 119071, Russia

[5] Mendeleev Univ Chem Technol Russia, Russian Acad Sci, Higher Chem Coll, 9 Miusskaya Sq, Moscow 125047, Russia

来源：

ORGANIC CHEMISTRY FRONTIERS | 2017年 / 4卷 / 10期

基金：

俄罗斯基础研究基金会;

关键词：

METAL-FREE; BOND FORMATION; 1,3-DICARBONYL COMPOUNDS; AEROBIC DIOXYGENATION; NITROXYL RADICALS; MICHAEL ADDITION; LEAVING GROUPS; OXYL RADICALS; HYDROXYPHTHALIMIDE; OXIDATION;

D O I：

10.1039/c7qo00447h

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Oxidative C-O coupling of pyrazolones with N-hydroxy compounds of different classes (N-hydroxyphthalimide, N-hydroxybenzotriazole, oximes) was achieved; both one-electron oxidants (Fe(ClO4)(3), (NH4)(2)Ce(NO3)(6)) and two-electron oxidants (PhI(OAc)(2), Pb(OAc)(4)) are applicable, and the yields reach 91%. Apparently, the coupling proceeds via the formation of N-oxyl radicals from N-hydroxy compounds. One of the N-oxyl intermediates, the diacetyliminoxyl radical, was found to be exclusively stable in solution in spite of being sterically unhindered; it was isolated from an oxidant and used as a new reagent for the synthesis and mechanism study. The products of C-O coupling of pyrazolones with N-hydroxyphthalimide can be easily transformed into aminooxy compounds, valuable substances for combinatorial chemistry.

引用

页码：1947 / 1957

页数：11

共 9 条

[1] Diacetyliminoxyl as a selective radical reagent for organic synthesis: dehydrogenation and dehydrogenative C-O coupling reactions
Budnikov, Alexander S.
Krylov, Igor B.
Kuzmin, Ilya V.
Segida, Oleg O.
Lastovko, Andrey V.
Shevchenko, Mikhail I.
Nikishin, Gennady I.
Terent'ev, Alexander O.
Organic Chemistry Frontiers, 2022, 10 (02) : 388 - 398
[2] Diacetyliminoxyl as a selective radical reagent for organic synthesis: dehydrogenation and dehydrogenative C-O coupling reactions
Terent'ev, Alexander O.
Krylov, Igor B.
Kuzmin, Ilya V.
Segida, Oleg O.
Lastovko, Andrey V.
Shevchenko, Mikhail I.
Nikishin, Gennady I.
Terent'ev, Alexander O.
ORGANIC CHEMISTRY FRONTIERS, 2023, 10 (02): : 388 - 398
[3] Iminoxyl Radical-Based Strategy for Intermolecular C-O Bond Formation: Cross-Dehydrogenative Coupling of 1,3-Dicarbonyl Compounds with Oximes
Krylov, Igor B.
Terent'ev, Alexander O.
Timofeev, Vladimir P.
Shelimov, Boris N.
Novikov, Roman A.
Merkulova, Valentina M.
Nikishin, Gennady I.
ADVANCED SYNTHESIS & CATALYSIS, 2014, 356 (10) : 2266 - 2280
[4] Metal-Free Cross-Dehydrogenative C-O Coupling of Carbonyl Compounds with N-Hydroxyimides: Unexpected Selective Behavior of Highly Reactive Free Radicals at an Elevated Temperature
Krylov, Igor B.
Lopat'eva, Elena R.
Budnikov, Alexander S.
Nikishin, Gennady I.
Terent'ev, Alexander O.
JOURNAL OF ORGANIC CHEMISTRY, 2020, 85 (04): : 1935 - 1947
[5] Consecutive cross-dehydrogenative C-O and C-N construction for the synthesis of polyarene with AIE properties under electrochemical condition involving oxygen radical species
Zhang, Zhicheng
Wen, Linzi
Xu, Shihai
Tang, Yu
Cao, Xiaohui
Feng, Pengju
GREEN CHEMISTRY, 2023, 25 (06) : 2287 - 2292
[6] Electrochemically Induced Synthesis of N-Allyloxyphthalimides via Cross-Dehydrogenative C-O Coupling of N-Hydroxyphthalimide with Alkenes Bearing the Allylic Hydrogen Atom
Paveliev, Stanislav A.
Segida, Oleg O.
Dvoretskiy, Andrey
Terent'ev, Alexander O.
ACS OMEGA, 2024, 9 (50): : 49825 - 49831
[7] Cobalt-catalyzed O-arylation of N-protected amino alcohols with arenes via cross-dehydrogenative C-O coupling strategy: Direct access to aryloxyamines
Wang, Chaoyu
Bei, Wenfeng
Li, Wanting
Wang, Dongwei
Liu, Yuqin
Gong, Zile
Zeng, Kailin
Feng, Ruokun
Huang, Xianqiang
Qi, Chenze
TETRAHEDRON LETTERS, 2022, 106
[8] Hidden Reactivity of Barbituric and Meldrum's Acids: Atom-Efficient Free-Radical C-O Coupling with N -Hydroxy Compounds
Krylov, Igor B.
Paveliev, Stanislav A.
Budnikov, Alexander S.
Segida, Oleg O.
Merkulova, Valentina M.
Vil, Vera A.
Nikishin, Gennady I.
Terent'ev, Alexander O.
SYNTHESIS-STUTTGART, 2022, 54 (02): : 506 - 516
[9] Heterogeneous Photocatalysis as a Potent Tool for Organic Synthesis: Cross-Dehydrogenative C-C Coupling of N-Heterocycles with Ethers Employing TiO2/N-Hydroxyphthalimide System under Visible Light
Lopat'eva, Elena R.
Krylov, Igor B.
Segida, Oleg O.
Merkulova, Valentina M.
Ilovaisky, Alexey I.
Terent'ev, Alexander O.
MOLECULES, 2023, 28 (03):

← 1 →