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Structure of 119165-69-4

Chemical Structure| 119165-69-4

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Product Citations

Qiao Lin ; Ethan H. Spielvogel ; Tianning Diao ;

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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Product Details of [ 119165-69-4 ]

CAS No. :119165-69-4
Formula : C8H8N2O
M.W : 148.16
SMILES Code : C1(C2=NCCO2)=NC=CC=C1
MDL No. :N/A
InChI Key :GBSQTQRZHMQHGH-UHFFFAOYSA-N
Pubchem ID :15426957

Safety of [ 119165-69-4 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P280-P301+P312-P302+P352-P305+P351+P338

Application In Synthesis of [ 119165-69-4 ]

* 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.

  • Upstream synthesis route of [ 119165-69-4 ]

[ 119165-69-4 ] Synthesis Path-Upstream   1~4

  • 1
  • [ 119165-69-4 ]
  • [ 16347-06-1 ]
YieldReaction ConditionsOperation in experiment
94% at 20℃; for 17 h; General procedure: To a solution of 2-(2’-pyridyl)-1,3-oxazoline (1, 37 mg, 0.25 mmol) and pyridine (80 L, 1.0 mmol) in H2O (6 mL), was added pyridinium hydrobromide perbromide (320 mg, 1.0 mmol) at room temperature. After stirring for 23 h at rt, the reaction mixture was treated with 0.5 M aq Na2S2O3 (10 mL), 1.0 M NaHCO3 (15 mL) and extracted with EtOAc (60 mL). The organic layer was washed with 0.5 M aq Na2S2O3 and successively washed with saturated aq NaCl, and dried over MgSO4. After removal ofsolvent in vacuo, the residue was purified by column chromatography on silica gel (Wako C-200) with CCl4, CCl4-CHCl3 (2:1 v/v). Cyanomethyl 2-pyridinecarboxylate (2, 38 mg, 0.23 mmol) was obtained in 92percent yield.
References: [1] Heterocycles, 2017, vol. 94, # 6, p. 1133 - 1142.
  • 2
  • [ 119165-69-4 ]
  • [ 84555-18-0 ]
  • [ 16347-06-1 ]
YieldReaction ConditionsOperation in experiment
72% at 20℃; for 21 h; General procedure: To a solution of 2-(2’-pyridyl)-1,3-oxazoline (1, 37 mg, 0.25 mmol) and pyridine (80 L, 1.0 mmol) in H2O (6 mL), was added pyridinium hydrobromide perbromide (320 mg, 1.0 mmol) at room temperature. After stirring for 23 h at rt, the reaction mixture was treated with 0.5 M aq Na2S2O3 (10 mL), 1.0 M NaHCO3 (15 mL) and extracted with EtOAc (60 mL). The organic layer was washed with 0.5 M aq Na2S2O3 and successively washed with saturated aq NaCl, and dried over MgSO4. After removal ofsolvent in vacuo, the residue was purified by column chromatography on silica gel (Wako C-200) with CCl4, CCl4-CHCl3 (2:1 v/v). Cyanomethyl 2-pyridinecarboxylate (2, 38 mg, 0.23 mmol) was obtained in 92percent yield.
25% at 20℃; for 17 h; General procedure: To a solution of 2-(2’-pyridyl)-1,3-oxazoline (1, 37 mg, 0.25 mmol) and pyridine (80 L, 1.0 mmol) in H2O (6 mL), was added pyridinium hydrobromide perbromide (320 mg, 1.0 mmol) at room temperature. After stirring for 23 h at rt, the reaction mixture was treated with 0.5 M aq Na2S2O3 (10 mL), 1.0 M NaHCO3 (15 mL) and extracted with EtOAc (60 mL). The organic layer was washed with 0.5 M aq Na2S2O3 and successively washed with saturated aq NaCl, and dried over MgSO4. After removal ofsolvent in vacuo, the residue was purified by column chromatography on silica gel (Wako C-200) with CCl4, CCl4-CHCl3 (2:1 v/v). Cyanomethyl 2-pyridinecarboxylate (2, 38 mg, 0.23 mmol) was obtained in 92percent yield.
References: [1] Heterocycles, 2017, vol. 94, # 6, p. 1133 - 1142.
[2] Heterocycles, 2017, vol. 94, # 6, p. 1133 - 1142.
  • 3
  • [ 119165-69-4 ]
  • [ 16347-06-1 ]
  • [ 717138-97-1 ]
YieldReaction ConditionsOperation in experiment
23% With pyridine; pyridinium perbromide hydrobromide In methanol at 20℃; for 16 h; General procedure: To a solution of 2-(2’-pyridyl)-1,3-oxazoline (1, 37 mg, 0.25 mmol) and pyridine (80 L, 1.0 mmol) in H2O (6 mL), was added pyridinium hydrobromide perbromide (320 mg, 1.0 mmol) at room temperature. After stirring for 23 h at rt, the reaction mixture was treated with 0.5 M aq Na2S2O3 (10 mL), 1.0 M NaHCO3 (15 mL) and extracted with EtOAc (60 mL). The organic layer was washed with 0.5 M aq Na2S2O3 and successively washed with saturated aq NaCl, and dried over MgSO4. After removal ofsolvent in vacuo, the residue was purified by column chromatography on silica gel (Wako C-200) with CCl4, CCl4-CHCl3 (2:1 v/v). Cyanomethyl 2-pyridinecarboxylate (2, 38 mg, 0.23 mmol) was obtained in 92percent yield.
References: [1] Heterocycles, 2017, vol. 94, # 6, p. 1133 - 1142.
  • 4
  • [ 119165-69-4 ]
  • [ 1121-60-4 ]
  • [ 84555-18-0 ]
  • [ 16347-06-1 ]
YieldReaction ConditionsOperation in experiment
23% at 20℃; for 14 h; General procedure: To a solution of 2-(2’-pyridyl)-1,3-oxazoline (1, 37 mg, 0.25 mmol) and pyridine (80 L, 1.0 mmol) in H2O (6 mL), was added pyridinium hydrobromide perbromide (320 mg, 1.0 mmol) at room temperature. After stirring for 23 h at rt, the reaction mixture was treated with 0.5 M aq Na2S2O3 (10 mL), 1.0 M NaHCO3 (15 mL) and extracted with EtOAc (60 mL). The organic layer was washed with 0.5 M aq Na2S2O3 and successively washed with saturated aq NaCl, and dried over MgSO4. After removal ofsolvent in vacuo, the residue was purified by column chromatography on silica gel (Wako C-200) with CCl4, CCl4-CHCl3 (2:1 v/v). Cyanomethyl 2-pyridinecarboxylate (2, 38 mg, 0.23 mmol) was obtained in 92percent yield.
References: [1] Heterocycles, 2017, vol. 94, # 6, p. 1133 - 1142.
 

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