65009-00-9

Usage

InChI:InChI=1/C11H15NO2/c1-3-12(4-2)11(13)14-10-8-6-5-7-9-10/h5-9H,3-4H2,1-2H3

Upstream product

• 102-09-0 bis(phenyl) carbonate 
• 109-89-7 diethylamine 
• 88-10-8 N,N-diethylcarbamyl chloride 
• 108-95-2 phenol 
• 124-38-9 carbon dioxide 
• 144930-49-4 1-2,4-dimethylphenyl-2-phenyliodonium triflate 
• 66003-76-7 Diphenyliodonium triflate 
• 6293-66-9 diphenyliodonium p-toluenesulfonate 
• 98-80-6 phenylboronic acid 
• 24388-23-6 2-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxoborole 
• 5123-13-7 5,5-dimethyl-2-phenyl-1,3,2-dioxaborinane 
• 10531-78-9 5-methyl-1,3-benzoxazole 
• 59722-32-6 (3-hydroxyphenyl)methanesulfonate 
• 617-84-5 N-formyldiethylamine 

Downstream Products

• 35580-98-4 O-(2-hydroxy)phenyl N,N-diethylcarbamate 
• 19311-91-2 N,N-diethylsalicylamide 
• 1025324-53-1 2-but-2-ynoylphenyl diethylcarbamate 
• 4096-20-2 N-phenyl piperidine 
• 118-93-4 o-hydroxyacetophenone 
• 610-99-1 1-(2-Hydroxy-phenyl)-propan-1-on 
• 2887-61-8 2-hydroxybutyrophenone 
• 18430-91-6 1-(2-hydroxyphenyl)pentan-1-one 
• 3226-15-1 1-(2-hydroxyphenyl)hexan-1-one 
• 22362-59-0 1-(2-hydroxyphenyl)heptan-1-one 
• 19019-21-7 1-(2-hydroxyphenyl)-3-methylbutan-1-one 
• 1660132-26-2 2-(((bis(trimethylsilyl)methyl)dimethylsilyl)oxy)-N,N-diethylbenzamide 
• 7420-86-2 5-methyl-2-phenyl-1,3-benzoxazole 
• 16155-94-5 6-methyl-2-p-tolylbenzoxazole 

Relevant academic research and scientific papers

Remarkably Efficient Iridium Catalysts for Directed C(sp2)-H and C(sp3)-H Borylation of Diverse Classes of Substrates

Here we describe the discovery of a new class of C-H borylation catalysts and their use for regioselective C-H borylation of aromatic, heteroaromatic, and aliphatic systems. The new catalysts have Ir-C(thienyl) or Ir-C(furyl) anionic ligands instead of the diamine-type neutral chelating ligands used in the standard C-H borylation conditions. It is reported that the employment of these newly discovered catalysts show excellent reactivity and ortho-selectivity for diverse classes of aromatic substrates with high isolated yields. Moreover, the catalysts proved to be efficient for a wide number of aliphatic substrates for selective C(sp3)-H bond borylations. Heterocyclic molecules are selectively borylated using the inherently elevated reactivity of the C-H bonds. A number of late-stage C-H functionalization have been described using the same catalysts. Furthermore, we show that one of the catalysts could be used even in open air for the C(sp2)-H and C(sp3)-H borylations enabling the method more general. Preliminary mechanistic studies suggest that the active catalytic intermediate is the Ir(bis)boryl complex, and the attached ligand acts as bidentate ligand. Collectively, this study underlines the discovery of new class of C-H borylation catalysts that should find wide application in the context of C-H functionalization chemistry.

N -Arylation of (hetero)arylamines using aryl sulfamates and carbamates via C-O bond activation enabled by a reusable and durable nickel(0) catalyst

An effective and general aryl amination protocol has been developed using a magnetically recoverable Ni(0) based nanocatalyst. This new stable catalyst was prepared on Fe3O4@SiO2 modified by EDTA and investigated by FT-IR, EDX, TEM, XRD, DLS, FE-SEM, XPS, NMR, TGA, VSM, ICP and elemental analysis techniques. The reaction proceeded via carbon-oxygen bond cleavage of (hetero)aryl carbamates and sulfamates under simple and mild conditions without the use of any external ligands. This method demonstrated functional group tolerance in the N-arylation of various nitrogen-containing compounds as well as aliphatic amines, anilines, pyrroles, pyrazoles, imidazoles, indoles, and indazoles with good to excellent yields. Furthermore, the catalyst could be easily recovered by using an external magnetic field and directly reused at least six times without notable reduction in its activity. This journal is

Experimental and computational study of the 1,5-o → n carbamoyl snieckus-fries-type rearrangement

The reactions of o-lithiated O-aryl N,N-diethylcarbamates with different C-N multiple bond electrophiles have been thoroughly studied. A 1,5-O → N carbamoyl shift, a new variation of the anionic Fries-type rearrangement, takes place when nitriles, imines, or alkylcarbodiimides are employed. In these cases, the carbamoyl group plays a dual role as a directing group, building up a variety of functional groups through the 1,5-O → N carbamoyl migration. On the other hand, the use of iso(thio)cyanates and arylcarbodiimides led to non-rearranged o-functionalized Oarylcarbamates. This reactivity was further computationally explored, and the governing factor could be traced back to the relative basicity of the alternative products (migrated vs nonmigrated substrates). This exploration also provided interesting insights about the degree of complexation of the lithium cations onto these substrates. A new access to useful 2-hydroxybenzophenone derivatives has also been developed.

Aryl Carbamates: Mechanisms of Orthosodiations and Snieckus-Fries Rearrangements

Aryl carbamates are orthometalated by sodium diisopropylamide (NaDA) in tetrahydrofuran. The resulting arylsodiums undergo Snieckus-Fries rearrangement to give orthoacylated phenols in good yield. The intermediate arylsodiums and resulting orthoacylated phenolates are suggested to be monomeric. The rate-limiting step in the two-step sequence depends on the steric demands of the carbamoyl moiety and the substituents in the meta position of the arene. Rate studies reveal a dominant disolvated-monomer-based orthometalation followed by a di- or trisolvated arylsodium monomer-based rearrangement. Kinetic evidence of a NaDA-catalyzed Snieckus-Fries rearrangement suggests the intermediacy of mixed trimers. Competitive halide eliminations to form benzyne are also discussed.

Aerobic C(sp2)-H Hydroxylations of 2-Aryloxazolines: Fast Access to Excited-State Intramolecular Proton Transfer (ESIPT)-Based Luminophores

The direct hydroxylation of 2-aryloxazolines via a deprotonative magnesiation using TMPMgCl·LiCl and subsequent oxidation with molecular oxygen or air as a green oxidant is reported. This method proceeds under mild conditions at room temperature with high regioselectivity and chemoselectivity. The obtained phenols exhibit tunable luminescence properties, induced by excited-state intramolecular proton transfer. This method opens a new opportunity for the sustainable synthesis of luminescent organic molecules.

Access to Biphenyls by Palladium-Catalyzed Oxidative Coupling of Phenyl Carbamates and Phenols

The oxidative cross-coupling of phenols (3 equiv) to various substituted phenyl N, N -diethylcarbamates was explored with a variety of substrates. Pd(OAc) 2 was employed as the catalyst (20 molpercent) and K 2 S 2 O 8

Directed ortho-Metalation of O-Aryl N,N-Dialkylcarbamates: Methodology, Anionic ortho-Fries Rearrangement, and Lateral Metalation

The directed ortho-lithiation reactions of O-aryl N,N-dialkylcarbamates as well as O-1-naphthyl and O-2-naphthyl N,N-dialkylcarbamates with sec-butyllithium/tetramethylethylenediamine (sBuLi/TMEDA) followed by quenching with various electrophiles afford a range of polysubstituted aromatic compounds. If the solutions of the ortho-lithiated carbamates are warmed to room temperature without the addition of external electrophiles, salicylamide and 1- and 2-hydroxynaphthamide derivatives are formed through anionic ortho-Fries rearrangements. The relative stabilities and reactivities of different O-aryl N,N-dialkylcarbamates were investigated. The lateral metalation of 2-tolyl carbamates with lithium diisopropylamide (LDA) provides a route to benzo[b]furan-2(3H)-ones. Previously reported results are used in a comparison of seven O-based directed metalation groups in reactions with several electrophiles. The described methodology is useful for the preparation of 1,2,3-substituted aromatic compounds.

1,5-O → N Carbamoyl Snieckus-Fries-Type Rearrangement

The reaction of o-lithiated O-aryl N,N-diethylcarbamates with (hetero)aromatic nitriles gives rise to functionalized salicylidene urea derivatives in high yields through a new 1,5-O → N carbamoyl migration. This Snieckus-Fries-type rearrangement nicely complements previously known O → C and O → O related shifts. In addition, when dimethylmalononitrile is used as the electrophilic partner, the carbamoyl shift is preferred over the expected transnitrilation reaction.

A copper-catalyzed oxidative coupling reaction of arylboronic acids, amines and carbon dioxide using molecular oxygen as the oxidant

A Cu-catalyzed oxidative coupling reaction of arylboronic acids, amines and carbon dioxide is described for the first time in this paper. The reaction tolerates a wide range of functional groups, providing a convenient protocol for the synthesis of various O-aryl carbamates. The successful development of the transformation was enabled by the use of BF3·OEt2 as the promoter and molecular oxygen as the oxidant. Mechanistic studies suggested that the CuII carbamato complex is involved in the catalytic transformation.

Nickel-catalyzed C?H arylation of benzoxazoles and oxazoles: Benchmarking the influence of electronic, steric and leaving group variations in phenolic electrophiles

Electronic, steric and leaving group effects for Ni-catalyzed direct arylations using C?O electrophiles were benchmarked. The scope of arylations with pivalates was general with respect to both the electronics on the electrophile and the azoles. Furthermore, the arylation of azoles with tosylates, mesylates and carbamates with varying electronics was explored, and showed electronic trends similar to those of the pivalate reactions. Finally, the relative rate of arylation of 5-methyl benzoxazole with two electronically-similar electrophiles bearing different leaving groups was established. The results from these studies implicate the following order of relative reactivity: mesylates>pivalates>carbamates.