Hypervalent iodine compounds for anti-Markovnikov-type iodo-oxyimidation of vinylarenes

• Igor B. Krylov,
• Stanislav A. Paveliev,
• Mikhail A. Syroeshkin,
• Alexander A. Korlyukov,
• Pavel V. Dorovatovskii,
• Yan V. Zubavichus,
• Gennady I. Nikishin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2018, 14, 2146–2155, doi:10.3762/bjoc.14.188

• radicals that is generated from an inexpensive N-hydroxyphthalimide (NHPI). This radical was used in various aerobic oxidations of bulk chemicals [18][19][43][44]. In the present work imide-N-oxyl radicals were used for the addition to the C=C bonds of styrenes with subsequent functionalization of the

• resulting benzylic radicals. Recently, the precursors of N-oxyl radicals, such as N-hydroxyphthalimide (NHPI), N-hydroxysuccinimide (NHSI), N-hydroxybenzotriazole (HOBt) and hydroxamic acids, have been used in the reactions of radical oxygenation of styrenes [45]. Growth of interest is observed concerning

• formation of C–I and C–O bonds, which implies the radical pathway of the reaction. The iodo-oxyimidation of styrenes was studied in the model reaction of styrene (1a) with N-hydroxyphthalimide (2a). During the optimization, the oxidant and the iodine source, as well as the nature of the solvent and the

Anomeric modification of carbohydrates using the Mitsunobu reaction

• Julia Hain,
• Patrick Rollin,
• Werner Klaffke and
• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2018, 14, 1619–1636, doi:10.3762/bjoc.14.138

• (6.3), N-hydroxyphthalimide was early considered in Mitsunobu reactions, for example by Grochowski and Jurczak to form an anomeric phthalimide–oxy bond as shown in several sugar series [109][110][111]. This gives access to new O-glycosylhydroxylamines, namely for the construction of glycosidic N–O

Oxidative dehydrogenation of C–C and C–N bonds: A convenient approach to access diverse (dihydro)heteroaromatic compounds

• Santanu Hati,
• Ulrike Holzgrabe and
• Subhabrata Sen

Beilstein J. Org. Chem. 2017, 13, 1670–1692, doi:10.3762/bjoc.13.162

• reaction was facilitated at room temperature by N-hydroxyphthalimide (NHPI) and cobalt acetate (Co(OAc)2) as catalysts in acetonitrile (Scheme 20). The reaction followed a free radical mechanism as exemplified by the oxidative dehydrogenation of DHPs. The initial step involved the formation of the

Transition-metal-catalyzed synthesis of phenols and aryl thiols

• Yajun Liu,
• Shasha Liu and
• Yan Xiao

Beilstein J. Org. Chem. 2017, 13, 589–611, doi:10.3762/bjoc.13.58

• did not work with ortho-substituted arenes. In 2013, Jiao and co-workers reported a hydroxylation protocol for (2-pyridyl)arenes using PdCl2 and N-hydroxyphthalimide (NHPI) as catalyst and molecular oxygen as oxidant [60]. (2-Pyridyl)arenes were converted to the hydroxylated products in toluene at 100

Base metal-catalyzed benzylic oxidation of (aryl)(heteroaryl)methanes with molecular oxygen

• Hans Sterckx,
• Johan De Houwer,
• Carl Mensch,
• Wouter Herrebout,
• Kourosch Abbaspour Tehrani and
• Bert U. W. Maes

Beilstein J. Org. Chem. 2016, 12, 144–153, doi:10.3762/bjoc.12.16

• conditions. Oxidations of this kind using Oxone® [10][11], NaOCl [12] or especially peroxides [13][14][15][16][17][18][19] as the terminal oxidant are quite numerous. However, transformations using molecular oxygen are rare. Ishii showed that organocatalysts such as N-hydroxyphthalimide (NHPI) in combination

Copper-catalyzed aminooxygenation of styrenes with N-fluorobenzenesulfonimide and N-hydroxyphthalimide derivatives

• Yan Li,
• Xue Zhou,
• Guangfan Zheng and
• Qian Zhang

Beilstein J. Org. Chem. 2015, 11, 2721–2726, doi:10.3762/bjoc.11.293

• Yan Li Xue Zhou Guangfan Zheng Qian Zhang Department of Chemistry, Northeast Normal University, Changchun 130024, China 10.3762/bjoc.11.293 Abstract A copper-catalyzed aminooxygenation reaction of styrenes with N-fluorobenzenesulfonimide and N-hydroxyphthalimide derivatives has been developed

• . The aminooxygenation product could be converted into the corresponding alcohol or free amine through the cleavage of the N–O or C–N bond of the N-hydroxyphthalimide moiety. Keywords: aminooxygenation of styrenes; copper catalysts; N-fluorobenzenesulfonimide; N-hydroxyphthalimide derivatives

• amination of allenes [46]. Encouraged by these results, we try to develop copper-catalyzed aminooxygenation of alkenes by using NFSI. Herein, we report a simple and efficient copper-catalyzed three-component aminooxygenation reaction of styrenes with NFSI and N-hydroxyphthalimide (NHPI) derivatives (Scheme

C–H bond halogenation catalyzed or mediated by copper: an overview

• Wenyan Hao and
• Yunyun Liu

Beilstein J. Org. Chem. 2015, 11, 2132–2144, doi:10.3762/bjoc.11.230

• a catalytic system consisting of (BPMED)CuI (copper(I) bisimine complex), N-hydroxyphthalimide (NHPI), KB(C6F5)4 and KI. The protocol allowed the selective fluorination of various substrates, including cycloalkanes and benzylic compounds using commercially available Selectfluor as fluorine source

Cross-dehydrogenative coupling for the intermolecular C–O bond formation

• Igor B. Krylov,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2015, 11, 92–146, doi:10.3762/bjoc.11.13

• [146]. The coupling reaction with N-hydroxyphthalimide (154b) was carried out using the NaI/aqueous t-BuOOH/KOH system instead of Bu4NI/t-BuOOH in decane [146]. The resulting activated esters 159 and 160 were isolated or used in the one-pot reaction with amines to prepare amides (Scheme 32). The

Metal-free aerobic oxidations mediated by N-hydroxyphthalimide. A concise review

• Lucio Melone and
• Carlo Punta

Beilstein J. Org. Chem. 2013, 9, 1296–1310, doi:10.3762/bjoc.9.146

• Abstract Since the beginning of the century, N-hydroxyphthalimide and related compounds have been revealed to be efficient organocatalysts for free-radical processes and have found ample application in promoting the aerobic oxidation of a wide range of organic substrates. When combined with different co

• the O2-mediated selective oxidation of organic compounds and looking for environmentally safe alternatives to metal catalysis. Keywords: autoxidation; free-radicals; metal-free; molecular oxygen; N-hydroxyphthalimide; Introduction The development of efficient and cheap catalytic systems for the

• detrimental for the selectivity of the process and they would not meet the standards of “green chemistry”. An alternative catalytic route is based on the use of N-hydroxy imides (NHIs), and in particular N-hydroxyphthalimide (NHPI), which have found ample application as ideal catalysts for the aerobic

Copper-catalyzed aerobic aliphatic C–H oxygenation with hydroperoxides

• Pei Chui Too,
• Ya Lin Tnay and
• Shunsuke Chiba

Beilstein J. Org. Chem. 2013, 9, 1217–1225, doi:10.3762/bjoc.9.138

• weak bond-dissociation enthalpies (i.e., tertiary alkyl C–H bonds, benzylic C–H bonds, etc.), by phthalimide N-oxyl radicals generated oxidatively from N-hydroxyphthalimide (NHPI), has been reported [20][21][22]. The resulting C-radicals could be trapped with molecular oxygen to form hydroperoxides. It

Thioester derivatives of the natural product psammaplin A as potent histone deacetylase inhibitors

• Matthias G. J. Baud,
• Thomas Leiser,
• Vanessa Petrucci,
• Mekala Gunaratnam,
• Stephen Neidle,
• Franz-Josef Meyer-Almes and
• Matthew J. Fuchter

Beilstein J. Org. Chem. 2013, 9, 81–88, doi:10.3762/bjoc.9.11

• hydroxylamine, followed by coupling with 6 using DCC and N-hydroxyphthalimide [27] as coupling reagents afforded thioacetate 8. The latter conditions were also applied to 5 and afforded thioacetate analogue 9. The isolated yields for products 8 and 9 were unoptimised, and our previous work suggests that these

• next step without further purification. To a solution of this crude oxime derivative in dioxane (10 mL/mmol) under argon was added DCC (1 equiv) and N-hydroxyphthalimide (1 equiv). After 2 hours of stirring at rt, 2-acetylsulfanylethylammonium chloride (6, 1 equiv) and triethylamine (2.1 equiv) were

• )ethyl ethanethioate (9) To a solution of acid 5 under argon in dioxane (5.5 mL/mmol) was added DCC (1 equiv), N-hydroxyphthalimide (1 equiv). After 2 hours of stirring at rt, 2-acetylsulfanylethylammonium chloride (6, 1 equiv) and triethylamine (2.1 equiv) were added and the resulting mixture was