Catalytic Hydroamination of Unsaturated Carbon‐Carbon Bonds

Brunet, Jean‐Jacques; Neibecker, Denis

doi:10.1002/3527600159.ch4

Cited by 139 publications

(53 citation statements)

References 151 publications

(204 reference statements)

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“…Although the NMR and X-ray data show that the acetylide complex 3 forms from the reaction of 1 and 4-pentyn-1-ol, we sought to determine if the alkoxide complex 4 is formed initially followed by rapid isomerization to 3. The reaction of 1 with 3 equiv of 4-pentyn-1-ol-d 1 (−OD) leads to the production of both CH 4 Although the kinetic product from the reaction of 1 with 4-pentyn-1-ol could not be unambiguously determined, the relative rates of reaction of 1 with phenylacetylene and ethanol are informative. The isolation of both (IPr)Cu(CCPh) and (IPr)Cu(OEt) have been reported.…”

Section: ■ Results and Discussionmentioning

confidence: 98%

Intramolecular Hydroalkoxylation and Hydroamination of Alkynes Catalyzed by Cu(I) Complexes Supported by N-Heterocyclic Carbene Ligands

et al. 2012

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Intramolecular addition of O−H and N−H bonds across carbon− carbon triple bonds to form 5-or 6-membered rings with exocyclic methylene groups for ether products and exocyclic methyl groups for imine products is catalyzed by (IPr)Cu(Me) (IPr = 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene). In a competition study, the cyclization of primary amines was found to be faster than that of alcohols. Kinetic studies for the conversion of 4-pentyn-1-ol reveal that the catalytic reaction is first-order in copper catalyst and zero-order in alkynyl alcohol, and an Eyring analysis yields ΔH ‡ = 18.7(4) kcal/ mol and ΔS ‡ = −26(1) eu. The reaction of 5-phenyl-4-pentyn-1-ol provides (Z)-2-benzylidene-tetrahydrofuran in high yield and with quantitative stereoselectivity. Results from combined experimental and DFT studies are consistent with a mechanism that involves alkyne insertion into a Cu−O alkoxide bond followed by protonolysis upon reaction with free alkynyl alcohol.

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Section: ■ Results and Discussionmentioning

confidence: 98%

Intramolecular Hydroalkoxylation and Hydroamination of Alkynes Catalyzed by Cu(I) Complexes Supported by N-Heterocyclic Carbene Ligands

et al. 2012

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“…Delightedly, the corresponding products ( 3x - 3z, 3aa-3ac ) were obtained in good to excellent yields with good functional group tolerance. In addition, given the prevailing existence of amines in pharmaceutical molecules and natural products (Ma et al., 2018a, Brunet and Neibecker, 2001), we selected Benzocaine ( 1ad , local anesthetic), Amoxapine ( 2ae , antidepressant), 2-(piperazin-1-yl)-4-(trifluoromethyl)pyrimidine ( 2af , medical/material intermediates), and multi-functional Vildagliptin ( 2ag , inhibit glucagon/chiral reagent/medicinalintermediate) and exposed them under the standard conditions; the corresponding products were obtained in 59%, 76%, 61%, and 71% yields, respectively. Gratifyingly, the chiral molecule ( S )- N -benzyl-1-phenylethan-1-amine ( 2ah ) experienced the optimal reaction conditions to deliver ( S , E )- N -benzyl- N′ -phenyl- N -(1-phenylethyl)formimidamide ( 3ah ) in 60% yield, which might be a potential chiral ligand to realize enantioselective-control reactions.…”

Section: Resultsmentioning

confidence: 99%

Chlorodifluoromethane as a C1 Synthon in the Assembly of N-Containing Compounds

Zhang

et al. 2019

iScience

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Summary The development of C1 synthons to afford the products that add one extra carbon has become an important research theme in the past decade, and significant progress has been achieved with CO 2 , CO, HCOOH, and others as C1 units. Despite the great advance, the search for new C1 synthons that display unique reactivity, complement to the current C1 sources, and add more value to C1 chemistry is still desirable. Herein, we report a quadruple cleavage of chlorodifluoromethane to yield a C1 source, which was successfully employed in the construction of various N -containing compounds especially with pharmaceutical molecules under mild conditions. This strategy provides a useful method for late-stage modification of pharmaceutical compounds. Four bonds in ClCF 2 H were orderly cleaved under basic conditions in the absence of transition metals. Preliminary mechanistic studies revealed that ( E )- N -phenylformimidoyl fluoride intermediate is involved in this process by in situ 1 H NMR studies and control experiments.

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“…Catalytic hydroamination, the direct formation of a new C-N bond by addition of the N-H bond to an unsaturated C-C function in the presence of a catalyst, is a subject of current interest both for fundamental research and for the chemical industry. [1][2][3] It is an atom-economical reaction constituting an interesting alternative entry to higher amines, which currently is mostly achieved by the catalyzed condensation of ammonia or amines with alcohols. 4 Since most primary alcohols are industrially produced from alkenes (hydroformylation-hydrogenation sequence), 5,6 the hydroamination process would suppress at least one step and avoid the coproduction of water.…”

Section: Introductionmentioning

confidence: 99%

Hydroamination of ethylene by aniline: catalysis in water

Dub¹,

Rodriguez‐Zubiri²,

Baudequin³

et al. 2010

Green Chem.

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The platinum-catalyzed and halide-promoted hydroamination of ethylene with aniline is reported for the first time in the presence of simple sodium halides in water. Compounds K 2PtX4 (X = Cl or Br), PtX2 or PtX4 (0.3% mol) in the presence of an aqueous solution of excess NaX and aniline under ethylene pressure (25 bar) affords N-ethylaniline with 60-85 turnovers after 10 h at 150 °C. The best result (TON = 85) was obtained in the presence of excess NaBr, whereas a slightly lower activity was observed with NaCl (60 cycles) and practically no activity with NaF or NaI (2 -4 cycles). The reaction also produces N,N-diethylaniline (up to 1 cycle) and 2-methylquinoline (up to 8 cycles) as by-products. The influence of added H + and different oxidizing agents was also examined.

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Catalytic Hydroamination of Unsaturated Carbon‐Carbon Bonds

Cited by 139 publications

References 151 publications

Intramolecular Hydroalkoxylation and Hydroamination of Alkynes Catalyzed by Cu(I) Complexes Supported by N-Heterocyclic Carbene Ligands

Intramolecular Hydroalkoxylation and Hydroamination of Alkynes Catalyzed by Cu(I) Complexes Supported by N-Heterocyclic Carbene Ligands

Chlorodifluoromethane as a C1 Synthon in the Assembly of N-Containing Compounds

Hydroamination of ethylene by aniline: catalysis in water

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