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Volumn , Issue 18, 2008, Pages 2841-2845

Directed palladium-catalyzed oxidative C-H arylation of (hetero)arenes with arylboronic acids by using TEMPO

Author keywords

Biaryls; Boronic acids; C H arylation; Nitroxides; Palladium

Indexed keywords

BORONIC ACID DERIVATIVE; CARBON; HYDROGEN; ISOTOPE; PALLADIUM; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; TEMPOL; THIOPHENE DERIVATIVE;

EID: 56849128233     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-0028-1083546     Document Type: Article
Times cited : (79)

References (45)
  • 1
    • 0000718373 scopus 로고    scopus 로고
    • (a) Pu, L. Chem. Rev. 1998, 98, 2405.
    • (1998) Chem. Rev , vol.98 , pp. 2405
    • Pu, L.1
  • 18
    • 33847802782 scopus 로고
    • For oxidative Heck coupling with arylboronic acids, see: a
    • For oxidative Heck coupling with arylboronic acids, see: (a) Dieck, H. A.; Heck, R. F. J. Org. Chem. 1975, 40, 1083.
    • (1975) J. Org. Chem , vol.40 , pp. 1083
    • Dieck, H.A.1    Heck, R.F.2
  • 30
    • 56849126095 scopus 로고    scopus 로고
    • Shi and Yu used Cu(II) salts as stoichiometric oxidants, see refs. 10 and 11.
    • Shi and Yu used Cu(II) salts as stoichiometric oxidants, see refs. 10 and 11.
  • 37
    • 56849094748 scopus 로고    scopus 로고
    • 4 and the volatiles were removed under reduced pressure. The residue was purified by flash chromatography.
    • 4 and the volatiles were removed under reduced pressure. The residue was purified by flash chromatography.
  • 41
    • 56849121928 scopus 로고    scopus 로고
    • Determination of the Kinetic Isotope Effects According to the general experimental procedure with 2-(2-deuterophenyl)pyridine (D-1, 39 mg, 0.25 mmol) and phenylboronic acid (122 mg, 1.00 mmol) for 72 h. Flash chromatography (pentane-EtOAc, 20:1 → 10:1) gave a mixture of 2a and D-2a as a yellow oil (17 mg, 65, The isotope effect was determined by integration of the ESI-HRMS data in consideration of the isotope pattern of 2a. The deuterated species D-2a and compound 2a were obtained in a ratio of 4.5:1. According to GP 1 with 2-ethoxy-2-phenylpyridine (6, 10 mg, 50 μmol, 2-(2-ethoxy-6-deuterophenyl)pyridine (D-6, 10 mg, 50 μmol) and phenylboronic acid (24 mg, 0.2 mmol) for 4 h. The ratios of D-6 to 6 (0.87:1) were determined before the reaction (0 h) and after a reaction time of 4 h (1.05:1) by integration of the corresponding ESI-HRMS data in consideration of the isotope pattern of 6. The k
    • Determination of the Kinetic Isotope Effects According to the general experimental procedure with 2-(2-deuterophenyl)pyridine (D-1, 39 mg, 0.25 mmol) and phenylboronic acid (122 mg, 1.00 mmol) for 72 h. Flash chromatography (pentane-EtOAc, 20:1 → 10:1) gave a mixture of 2a and D-2a as a yellow oil (17 mg, 65%). The isotope effect was determined by integration of the ESI-HRMS data in consideration of the isotope pattern of 2a. The deuterated species D-2a and compound 2a were obtained in a ratio of 4.5:1. According to GP 1 with 2-ethoxy-2-phenylpyridine (6, 10 mg, 50 μmol), 2-(2-ethoxy-6-deuterophenyl)pyridine (D-6, 10 mg, 50 μmol) and phenylboronic acid (24 mg, 0.2 mmol) for 4 h. The ratios of D-6 to 6 (0.87:1) were determined before the reaction (0 h) and after a reaction time of 4 h (1.05:1) by integration of the corresponding ESI-HRMS data in consideration of the isotope pattern of 6. The kinetic isotope effect was calculated to be 1.21.
  • 42
    • 56849114350 scopus 로고    scopus 로고
    • As a side product the doubly arylated product is always formed <15% with respect to the monoarylated compound, We assume that the primary kinetic isotope effect for the second arylation and the first arylation should be similar. Therefore, the measured value of 4.5 is slightly too high since 2a is consumed faster than D-2a. However, the error should be smaller than 12, Hence the primary kinetic isotope effect for the first arylation is about 4.0-4.5 to 1
    • As a side product the doubly arylated product is always formed (<15% with respect to the monoarylated compound). We assume that the primary kinetic isotope effect for the second arylation and the first arylation should be similar. Therefore, the measured value of 4.5 is slightly too high since 2a is consumed faster than D-2a. However, the error should be smaller than 12%. Hence the primary kinetic isotope effect for the first arylation is about 4.0-4.5 to 1.
  • 43
    • 56849085819 scopus 로고    scopus 로고
    • 2-(2,6-Dideuterophenyl)pyridine (D2-1) and 2-(2,6-Dibromophenyl)pyridine 2-(2-Bromophenyl)pyridine22 (466 mg, 2.0 mmol, Cu(OAc)2 (363 mg, 2.0 mmol, and 1,1,2,2-tetra- bromoethane were heated in a sealed reaction tube at 130°C for 24 h. 23 Dichloromethane (10 mL) and Na2S (aq sat, 10 mL) were added. The mixture was filtered over Celite and the filtrate was washed with brine (2 x 10 mL, The combined organic layers were dried over MgSO4 and the volatiles were removed under reduced pressure. The residue was purified by flash chromatography (pentane-MTBE, 20:1, 2-(2-Bromo-6-deuterophenyl) pyridine To a solution of 2-(2,6-dibromophenyl)pyridine (313 mg, 1.0 mmol) in THF (20 mL) at -78°C was added dropwise n-BuLi (1.68 M solution in hexanes, 0.60 mL, 1.00 mmol).23 The mixture was stirred for 30 min. Then, D2O (2.0 mL) was added and stirring was continued for additional 30
    • 3)


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