Citation: Jin-Fu Dong, Xin Yu, Cheng-Qing Ning, Liang Hu, Nie-Fang Yu. Selective mono-arylation in palladium-catalyzed cross-coupling reaction of dichlorotriazines with phenylboronate ester derivatives[J]. Chinese Chemical Letters, ;2013, 24(01): 41-44. shu

Selective mono-arylation in palladium-catalyzed cross-coupling reaction of dichlorotriazines with phenylboronate ester derivatives

1.
a School of Pharmaceutical Sciences, Central South University, Changsha 410013, China;
2.
b School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China

Corresponding author: Nie-Fang Yu,
Received Date: 15 October 2012
Available Online: 27 November 2012

Palladium-catalyzed cross-coupling reaction between dichlorotriazines and phenylboronate esters produced the mono-arylated triazines selectively and thus,the corresponding phenyltriazine derivatives could be assembled efficiently in moderate to good overall yields(50-80%).
- Suzuki cross-coupling reaction,
- Dichlorotriazines,
- Aryl boronic esters,
- Pd(PPh₃)₄
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  [26] Typical reaction procedures:In a 100 mL flask equipped with a magnetic stirring bar were charged with diclorotriazine(1.2 mmol),K₃PO₄·3H₂O(1.05 mmol), arylboronic esters(1.0 mmol)and Pd(PPh₃)₄(0.1 mmol)sequentially.The flask was attached to an argon line and the reaction was initiated by the addition of 10 mL dioxane/water mixture(10:1).The mixture was vigorously stirred for 1.2 h at 70 ℃.After cooling,the reaction mixture was concentrated under reduced pressure to dryness.Water was added,the aqueous suspension was extracted with DCM and the combined organic extracts were dried under MgSO₄ and concentrated.The residue was purified by preparative RP-HPLC to afford the product.
27. [27]
  [27] Representative spectroscopic data:(a)Spectral data for compound 6a: ¹H NMR (400 MHz,CDCl₃): δ 1.8-1.73(m,6 H),1.98-1.97(d,6 H,J=2.4 Hz),2.55(s,2 H), 2.55(br,4 H),3.58(s,2 H),4.05-3.92(br,4 H),7.44-7.28(m,6 H),8.18-8.10(m,3 H).¹³C NMR(100 MHz,CDCl₃): δ 28.1,31.6,36.4,39.3,41.6,43.7,43.8,52.6,52.7, 62.9,119.8,124.4,127.4,128.4,129.2,135.7,137.5,138.5,164.4,170.8,171.7, 176.2;HRMS(ESI):m/z[M+H] ⁺ calcd.for C₃₁H₃₆ClN₆O,543.2639;found 543.2625.
28. [28]
  (b)Spectral data for compound 8f:¹H NMR(400 MHz,DMSO-d₆): δ 3.30(br,4 H),3.43(br,4 H),4.34(s,2 H),4.64(d,2 H,J=5.2 Hz),5.43-5.25(m,2 H),6.08-5.99(m,1 H),7.24-7.21(m,1 H),7.51-7.42(m,6 H),7.94-7.84(m,2 H);¹³C NMR(100 MHz,DMSO-d₆): δ 50.5,50.6,59.6,68.9,114.8,118.2,120.1,121.6, 129.4,130.1,130.5,131.7,133.9,136.0,158.9,164.8,170.7,171.9;HRMS(ESI): m/z[M+H] ⁺calcd.for C₂₃H₂₅ClN₅O,422.1748;found 422.1636.
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沈阳化工大学材料科学与工程学院沈阳 110142