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With copper(l) iodide; N,N,N,N,-tetramethylethylenediamine; triethylamine at 20℃; for 1h; Schlenk technique; Inert atmosphere;
1,3-Diphenylprop-2-yn-1-one (3a); Typical Procedure
General procedure: An oven-dried Schlenk reaction tube equipped with a magnetic stirrer bar and a Teflon stopcock was evacuated while hot and allowed to cool under N2. The tube was first charged with CuI (0.02 mmol), TMEDA (0.05 mmol), and benzoyl chloride (1.2 mmol), follow byphenylacetylene (1 mmol) and Et3N (3.0 mmol). The mixture wasthen stirred at r.t. for 1 h under N2. When the reaction was complete, sat. aq NaHCO 3 (5 mL) and EtOAc (20 mL) were added. The reaction system was allowed to partition, and the organic phase was dried with Na2SO4, filtered, and concentrated on a rotary evaporator. The residue was purified by chromatography (silica gel) to give the cross-coupling product 3a (185.4 mg, 90%) as a white solid.
90%
With triethylamine; copper(l) chloride In toluene at 80℃; for 8h;
88%
With palladium diacetate; N-ethyl-N,N-diisopropylamine In dichloromethane at 100℃; for 0.5h;
88%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 20℃;
86%
With silica gel; N-ethyl-N,N-diisopropylamine; zinc dibromide at 20℃; for 2h;
3. General procedure for the synthesis of ynones
A test-tube was charged with the acyl chloride (1.2 mmol), a terminal alkyne (1.0 mmol), ZnBr2/SiO2 (0.1 g, 0.12 mmol), and DIPEA (1.2 mmol). The mixture was stirred at room temperature for 2 h under anhydrous conditions. Upon completion of the reaction (monitored by TLC), the mixture was extracted with EtOAc (3 × 5 mL). The organic layers were combined and washed with H2O (2 × 5 mL) to remove the amine hydrochloride formed during the reaction. The organic layer was separated, dried over anhydrous MgSO4, filtered, and concentrated under vacuum to give the product which was further purified by column chromatography using hexane/EtOAc (20:1) as eluent.
74%
With triethylamine at 20℃; for 0.25h;
95 %Chromat.
With pyridine In toluene at 20℃; for 0.5h; Aerobic conditions;
With copper(l) iodide; N,N,N,N,-tetramethylethylenediamine; triethylamine at 20℃; for 1h; Schlenk technique; Inert atmosphere;
With oxygen; nitrogen(II) oxide In acetonitrile at 20℃;
89%
With manganese(IV) oxide In acetone at 20℃; for 0.5h; Inert atmosphere;
With manganese(IV) oxide In dichloromethane for 2h; Reflux;
With manganese(IV) oxide In dichloromethane at 20℃;
II. Preparation of Alkynone Substrates
General procedure: To a solution of the above alkynol in anhydrous DCM (0.25 M) was addedMnO2 (10.0 equiv.) at room temperature. The reaction mixture was stirred atroom temperature until alkynol disappeared monitored by TLC. The solidMnO2 was removed by filtration of the reaction mixture through a pad of celite.Then it was extracted with ethyl acetate and dried with anhydrous Na2SO4.Then the reaction mixture was concentrated under reduced pressure andpurified by column chromatography to give the pure product.[2]Note: MnO2 was activated at 100 oC for 2 h and then cooled to room temperaturefor use.
With [1,4'-Bis(2'-diphenylphosphino-3'-methylimidazolio)butane]dichloridopalladium(II) triflate; triethylamine; N-butylpyridinium tetrafluoroborate at 100℃; for 2h;
With bis-[1-(5’-diphenylphosphinothiazol-2’-yl)-imidazolyl]dichloropalladium(II); triethylamine In N,N-dimethyl-formamide at 90℃; for 1.5h; Autoclave;
General procedure for carbonylative Sonogashira reaction
General procedure: In a typical experiment, the isolated crystalline precatalyst 1A (or 2A, 0.005 mmol) was sequentially mixed with 3 mL of solvent (DMF or [Bmim]PF6 if required), iodobenzene (5mmol), phenylacetylene (6 mmol), and Et3N (7.5 mmol). The obtained mixture was placed in a sealed Teflon-lined stainless steel autoclave, purged with syngas (CO, 1.0 MPa) and then stirred vigorously at the required temperature for the appointed time. Upon completion of the reaction, the mixture wasc ooled to room temperature and the pressure was carefully released. The reaction mixture was extracted with diethyl ether(5 mL 3). The ether fractions were combined and then analyzedby GC to determine the conversion of PhI (1-dodecane as an internal standard) and the selectivity for the carbonylative products (normalization method). The structures of the carbonylative products were further confirmed by GC-MS.
With ammonium peroxydisulfate; silver(I) acetate In water; dimethyl sulfoxide at 50℃; for 3h;
24 Example 14 to 29
General procedure: A-keto acid (1.1 mmol), aryl acetyl acid (1 mmol, R2 = H), AgOAc (5 mol%) and(NH4) 2S2O8 (2 mmol) was dissolved in a mixed solvent of DMSO (1 mL) and H2O (1 mL), and then stirred at 50 ° C for 3 hours under an air atmosphere.After the reaction was completed, it was extracted three times with Et 2 O (5 mL).The organic phases were combined and concentrated under reduced pressure.The obtained crude product was subjected to column chromatography (300-400 mesh silica gel, petroleum ether and ethyl acetate as eluent) to give the desired product.The substrate used and the reaction results are shown in Table 2.
With bis(cyclopentadienyl)titanium dichloride; isophthalic acid In ethanol at 20℃; for 12h; Green chemistry;
4.1. General procedure for recycling tests
General procedure: A reactor equipped with a magnetic stirring bar was charged with 1,3-ynone (103 mg, 0.5 mmol), o-phenylenediamine (64.8 mg, 0.6 mmol), Cp2TiCl2 (2.48 mg, 0.01 mmol), m-phthalic acid (1.66 mg, 0.01 mmol) and EtOH (0.5 mL). Then, the reaction system reacts with magnetic stirring at room temperature. After 12 h, the reaction was transferred to ice water to cool down; the precipitate, which is the expected product, was then filtered and washed twice with ice EtOH (2 mL). The filtrate was then concentrated to 0.5 ml under vacuum and used for a new catalytic run: 1,3-ynone (0.5 mmol), o-phenylenediamine (0.6 mmol) were introduced. The tube was stirred for the required time period
1-nitro-3-(3-phenylprop-2-yn-1-yl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
57%
With tris(pentafluorophenyl)borate; phenylsilane In acetonitrile at 30℃; for 72h; regioselective reaction;
III. Reduction of Alkynone Substrates General procedure I for standard conditions:
General procedure: To a solution of the alkynones (0.1 mmol, 1.0 equiv.) in MeCN (1 mL) was addedPhSiH3 (0.15 mmol, 1.5 equiv.) and B(C6F5)3 (5 mol%). The mixture was stirredat 30 oC for 3 days. Then the reaction mixture was concentrated under reducedpressure and purified by column chromatography to give the pure product.
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