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Qiao Lin ; Ethan H. Spielvogel ; Tianning Diao Chem,2023,9(5):1295-1308. DOI: 10.1016/j.chempr.2023.02.010
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Abstract: The capture of carbon-centered radicals at a nickel(II) center is commonly featured in recent cross-coupling and metallaphotoredox catalytic reactions. Despite its widespread application in catalysis, this fundamental step lacks experimental characterization. This report portrays radical capture at catalytically relevant nickel(II) centers from several aspects, including the structure-activity relationships of the ligands, the mechanism, the kinetics, and the stereoselectivity. Spectroscopic data provide evidence for the formation of a nickel(III) intermediate. Strikingly different reactivity between nickel-aryl and nickel-alkyl complexes implies different rate-determining steps for C(sp3)–C(sp3) and C(sp2)–C(sp3) bond formation. Kinetic data benchmark the capture rates on the scale of 10[7] M?1s?1 and 10[6] M?1s?1 for primary and secondary radicals, respectively. Overall, the activation energy is higher than that of previous computational estimations. Finally, stoichiometric experiments with well-defined chiral nickel complexes demonstrate that the radical trapping step can confer diastereoselectivity and enantioselectivity with a drastic ligand effect.
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CAS No. : | 3395-91-3 | MDL No. : | MFCD00000250 |
Formula : | C4H7BrO2 | Boiling Point : | - |
Linear Structure Formula : | Br(CH2)2CO2CH3 | InChI Key : | KQEVIFKPZOGBMZ-UHFFFAOYSA-N |
M.W : | 167.00 | Pubchem ID : | 76934 |
Synonyms : |
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Chemical Name : | Methyl 3-bromopropanoate |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H227-H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71.7% | In diethyl ether; at -20℃; for 1h;Inert atmosphere; | In a 250 mL round bottom flask, methyl 3-bromopropanoate (5.0 mL, 45.8 mmol, 1.0 eq.) was taken up in dry ether (55.2 mL, 0.83 M) under nitrogen and cooled to -20 C. To this, 3.0 M methylmagnesium bromide (45.8 ml, 137 mmol, 3.0 eq) was added in dropwise fashion and the resulting mixture was stirred for an hour. The reaction was quenched with aqueous ammonium chloride. The resulting white suspension was extracted with ether multiple times. The combined organics were washed with brine, dried over MgSO4, and concentrated to yield 4-bromo-2-methylbutan-2-ol as an oil (5.49 g, 71.7%) |
65% | In diethyl ether; at 0 - 20℃; for 2h; | To a stirred solution of 4-bromo-butyric acid methyl ester (2 g, 12.27 mmol) in diethyl ether (20 mL) is added methyl magnesium bromide (16.4 mL, 49.08 mmol) at 0 C. and the mixture is stirred at room temperature for 2 hours. The reaction mixture is quenched with 1 N HCl and extracted with diethyl ether (2*20 mL). The combined organic extracts are washed with saturated brine solution (20 mL), dried over sodium sulphate, filtered, and concentrated. The crude material is purified with silica gel column chromatography (combiflash) eluting in 20% EtOAc/hexanes to give the title compound (1.3 g, 65%). 1H NMR (400 MHz, CDCl3): δ 3.48 (t, J=8.0 Hz, 2H), 2.16 (t, J=7.4 Hz, 2H), 1.89 (s, 6H), 1.76 (s, 3H), 1.27 (s, 6H). |
60% | In diethyl ether; at 0 - 20℃; for 1h; | To a stirred solution of 4-bromo-butyric acid methyl ester (1 g, 5.9 mmol) in diethyl ether (20 mL) is added methyl magnesium bromide (19.9 mL, 23.9 mmol) at 0 C and the mixture is stirred at room temperature for 1 hour. The reaction mixture is quenched with aqueous ammonium chloride (40 mL) and extracted with diethyl ether (2x20 mL). The combined organic extracts are washed with saturated brine solution (20 mL), dried over sodium sulphate, filtered, and concentrated. The crude material is purified by silica gel column chromatography (combiflash) eluting with 20%EtOAc/hexanes to obtain title compound as pale pink liquid (0.6 g, 60%). ^NMR (400 MHz, DMSO) δ 4.38 (s, 1H), 3.52-3.48 (m, 2H), 1.97-1.91 (m, 2H), 1.08 (s, 6H). |
48.9% | In tetrahydrofuran; at 0 - 20℃; for 16h; | a) 4-Bromo-2-methylbutan-2-olTo a solution of methyl 3-bromopropanoate (5.0 g, 29.94 mmol, and 1.0 eq) in dry THF was added methyl magnesium bromide at 0C. The mixture was stirred at RT for 16 h and quenched and extracted as in Intermediate Example 5(c). The solvent was distilled off to afford the crude residue which was purified by column chromatography (60-120 silica gel, 50 % ethyl acetate in hexane). Yield 48.9 % (2.4 g). LC-MS (ESI): Calculated mass: 167.0; Observed massl67.1 [M+H]+ (it: 0.8-1.0 min). |
48.9% | In tetrahydrofuran; at 0 - 20℃; for 16h; | To a solution of methyl 3-bromopropanoate (5.0 g,29.94 mmol, and 1.0 eq) in dry THF was added methyl mag21 nesium bromide at 0 C. The mixture was stirred at RT for 16 h and quenched and extracted as in Intermediate Example 5(c). The solvent was distilled off to afford the crude residue which was purified by column chromatography (60-120 silica gel, 50% ethyl acetate in hexane). Yield 48.9% (2.4 g). LCMS (ESI): Calculatedmass: 167.0; Observedmass 167.1[M+ H] (it: 0.8-1.0mm). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In N-methyl-acetamide; | Step A: 4-Chloro-2-(2-methoxy-1-methyl-2-oxoethoxy)-benzoic acid, methyl ester A solution of <strong>[22717-55-1]methyl 4-chlorosalicylate</strong> (5.0 g) in dimethylformamide (10 ml) was treated sequentially with methyl 3-bromopropionate (4.0 g) and potassium carbonate (6.0 g). The mixture was stirred at room temperature for 18 hrs and diluted with water. The mixture was extracted with ether and the organics were washed with water. The organic layer was dried and evaporated to give the desired material (6.7 g) as a low melting solid. NMR: 7.8 (d, 1H), 7.2 (m 1H), 6.9 (m, 1H), 4.8 (q, 1H), 3.9 (s, 3H), 3.8 (s, 3H), 1.7 (d, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydride; In N,N-dimethyl-formamide; at 20 - 130℃; for 6h; | To a 100-mL round-bottomed flask containing 3-bromosaccharin (1.0 g, 3.8 mmol,Synthelee) in DMF (5 mL), was slowly added NaH (0.15 g, 3.8 mmol, 60percent in mineral oil, Aldrich) at room temp. Methyl 3-bromo-propanoate (2.1 mL, 19 mmol, Aldrich) was added and the reaction mixture was refluxed at 130 °C for 6 h. The reaction was quenched with water (15 mL) and the compound was extracted with EtOAc (2x20 mL). The organic phase was washed with 5percent brine (2x 10 mL), dried over Na2SO4, filtered, and concentrated. Purification EPO <DP n="124"/>with column chromatography over silica gel with hexane:EtOAc:MeOH (5:5:1) gave the title compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1-(Tert-butyl) 3-methyl azetidine-1,3-dicarboxylate (1 equiv.) is dissolved in dry tetrahydrofuran and cooled to-78 C. A solution of lithium hexamethyldisilazide (1.0 M in tetrahydrofuran) (1.1 equiv.) is then added dropwise and the solution is stirred for 1 hour. Methyl 3-bromopropanoate (1 equiv.) was then added dropwise. The is allowed to stir for 30 minutes and is then warmed gradually to room temperature. When the reaction is judged to be complete based on TLC or LCMS analysis, it is quenched with saturated aqueous ammonium chloride solution and diluted with ethyl acetate. The organic layer is separated and the aqueous layer is extracted with ethyl acetate (3x). The combined organic layers are washed with brine and dried over sodium sulfate before concentrating under reduced pressure. The crude product is then purified on silica providing 1-(tert-butyl) 3-methyl 3-(3-methoxy-3-oxopropyl)azetidine-1,3-dicarboxylate (Synlett, 2015, 26, 1815-1818.). |
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