3077-16-5

Usage

Synthesis Reference(s)

Tetrahedron Letters, 8, p. 293, 1967 DOI: 10.1016/S0040-4039(00)71537-1

InChI:InChI=1/C11H15NO/c1-10-2-4-11(5-3-10)12-6-8-13-9-7-12/h2-5H,6-9H2,1H3

Upstream product

• 106-49-0 p-toluidine 
• 111-46-6 diethylene glycol 
• 110-91-8 morpholine 
• 5720-05-8 4-methylphenylboronic acid 
• 29540-83-8 p-tolyl triflate 
• 591-17-3 meta-bromotoluene 
• 106-38-7 para-bromotoluene 
• 37828-58-3 lithium morpholide 
• 106-43-4 para-chlorotoluene 
• 23328-69-0 4-chloromorpholine 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 3899-96-5 4-methylphenyl tosylate 
• 4394-85-8 4-morpholinecarboxaldehyde 
• 13368-42-8 4-(trimethylsilyl)morpholine 

Downstream Products

• 1415461-03-8 1-(5-methyl-2-morpholinophenyl)naphthalen-2-ol 
• 602-09-5 1,1'-bi-2-naphthol 
• 28276-93-9 2-(p-toluidino-N-formyl)ethyl formate 

Relevant academic research and scientific papers

Polyisobutylene-supported N-heterocyclic carbene palladium catalysts

This paper describes how the nonpolar polymer polyisobutylene (PIB) can be used as a handle to prepare PIB-bound NHC ligands that are soluble in monophasic mixtures of mixed solvents but phase separable when such solvent systems are perturbed to be biphas

An improved synthesis of bis(1,3-di-N-tert-butylimidazol-2-ylidene)palladium(0) and its use in C-C and C-N coupling reactions

A new, improved synthesis of [Pd{CN(tBu)(CH)2N(tBu)}2] (1) and its use as a catalyst in coupling reactions, including aminations, is presented. An interesting side product formed in the synthesis of 1, [Pd(η3-C4H7){(CN(tBu)(CH) 2N(tBu)}Cl] (2), is also discussed.

Recyclable polymer-supported Pd catalysts for aryl amination reactions

Polymer-supported palladium catalysts were prepared from three commercially available phosphine-functionalised polymers (PS-PR2), Pd 2(dba)3 and P(t-Bu)3. Catalyst stability was investigated using VT 31/su

Catalytic Amination of Phenols with Amines

Given the wide prevalence and ready availability of both phenols and amines, aniline synthesis through direct coupling between these starting materials would be extremely attractive. Herein, we describe a rhodium-catalyzed amination of phenols, which provides concise access to diverse anilines, with water as the sole byproduct. The arenophilic rhodium catalyst facilitates the inherently difficult keto–enol tautomerization of phenols by means of π-coordination, allowing for the subsequent dehydrative condensation with amines. We demonstrate the generality of this redox-neutral catalysis by carrying out reactions of a large array of phenols with various electronic properties and a wide variety of primary and secondary amines. Several examples of late-stage functionalization of structurally complex bioactive molecules, including pharmaceuticals, further illustrate the potential broad utility of the method.

Cu(I)–N-heterocyclic carbene-catalyzed base free C–N bond formation of arylboronic acids with amines and azoles

A new N-heterocyclic carbene (NHC) precursor of imidazolium chloride and its corresponding Cu(I)–NHC complex 1 was synthesized. The complex 1 was found to be a highly effective catalyst for Chan-Evans-Lam coupling of arylboronic acid with amines and azoles (including imidazole, pyrazole and triazole), without addition of base at room temperature. Various substituents on three substrates can be tolerated, giving the desired coupling products in good to excellent yields (62–94%). The method is practical and offers an alternative to the corresponding copper-catalyzed Chan-Evans-Lam process for the construction of C–N bonds.

Product selective reaction controlled by the combination of palladium nanoparticles, continuous microwave irradiation, and a co-existing solid; ligand-free Buchwald-Hartwig aminationvs.aryne amination

We have developed a continuous microwave irradiation-assisted Buchwald-Hartwig amination using our original Pd nanoparticle catalyst with a copper plate as a co-existing metal solid. In this methodology, a microwave-controlled product selectivity was achieved between Buchwald-Hartwig amination and aryne amination performed under strongly basic conditions and at a high reaction temperature, because a polar chemical species such as Ar-Pd-halogen might be activated selectively by microwave radiation. Moreover, our catalyst could be used repeatedly over 10 times, and the amount of Pd leaching could be suppressed to a low level.

Effect of Precatalyst Oxidation State in C-N Cross-Couplings with 2-Phosphinoimidazole-Derived Bimetallic Pd(I) and Pd(II) Complexes

We report the catalytic activity of two phosphinoimidazole-derived bimetallic palladium complexes in Pd-catalyzed amination reactions. Our studies demonstrate that the starting oxidation state (Pd(I) or Pd(II)) of the dimeric complex has a significant effect on the efficiency of the catalytic reaction. The corresponding Pd(I) complex shows higher reactivity in Buchwald-Hartwig aminations, while the Pd(II) complex is much more reactive in carbonylative amination reactions. These new dimeric palladium complexes provide good to excellent reactivity and yields in the amination reactions tested.

Nickel-Catalyzed Intramolecular 1,2-Aryl Migration of Mesoionic Carbenes (iMICs)

Intramolecular 1,2-Dipp migration of seven mesoionic carbenes (iMICAr) 2 a–g (iMICAr=ArC{N(Dipp)}2CHC; Ar=aryl; Dipp=2,6-iPr2C6H3) under nickel catalysis to give 1,3-imidazoles (IMDAr) 3 a–g (IMDAr=ArC{N(Dipp)CHC(Dipp)N}) has been reported. The formation of 3 indicates the cleavage of an N?CDipp bond and the subsequent formation of a C?CDipp bond in 2, which is unprecedented in NHC chemistry. The use of 3 in accessing super-iMICs (5) (S-iMIC=ArC{N(Dipp)N(Me)C(Dipp)}C) has been shown with selenium (6), gold (7), and palladium (8) compounds. The quantification of the stereoelectronic properties reveals the superior σ-donor strength of 5 compared to that of classical NHCs. Remarkably, the percentage buried volume of 5 (%Vbur=45) is the largest known amongst thus far reported iMICs. Catalytic studies show a remarkable activity of 5, which is consistent with their auspicious stereoelectronic features.

Synthesis of N-heterocyclic carbene-Pd(II)-5-phenyloxazole complexes and initial studies of their catalytic activity toward the Buchwald-Hartwig amination of aryl chlorides

Three new N-heterocyclic carbene (NHC)-Pd(II) complexes using 5-phenyloxazole as the ancillary ligand have been obtained in moderate to good yields by a one-pot reaction of the corresponding imidazolium salts, palladium chloride and 5-phenyloxazole under mild conditions. Initial studies showed that one of the complexes is an efficient catalyst for the Buchwald-Hartwig amination of aryl chlorides with various secondary and primary amines under the varied catalyst loading of 0.01-0.05 mol%, thus it will enrich the chemistry of NHCs and give an alternative catalyst for the coupling of challenging while cost-low aryl chlorides.

A Tetraarylpyrrole-Based Phosphine Ligand for the Palladium-Catalyzed Amination of Aryl Chlorides

A tetraarylpyrrole-based phosphine ligand L1 in combination with Pd(dba)2 provided a catalyst for the Buchwald-Hartwig amination reaction. A variety of amines were rapidly coupled with aryl chlorides at a Pd loading of 0.5 mol%. The selective monoarylation of aliphatic primary amines was achieved in the presence of 0.8 equiv. water. Comparison experiments were also conducted, which revealed that the catalytic activity of L1 is superior to representative phosphine ligands in the Pd-catalyzed C?N coupling of various amines. (Figure presented.).