Mendeleev Commun., 2020, 30, 231–232
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2020.03.034.
H
BnO
Br
BnO
N
O
N
N
i
iii
iii
N
N
N
N
Br
HN
References
4
4' (89%)
6 (34%)
7 (30%)
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AcHN
AcHN
H2N
Br
ii
N
N
Br
HN
5
5' (60%)
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pyrrolylhetarenes 6 and 7 in 34 and 30% yields, respectively.§
As expected TBDPS protecting group was removed under the
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a dry ice bath to –78 °C. Then, BuLi (1.6 m in hexane, 6.4 ml, 10.2 mmol)
was added dropwise in an argon stream over 2 h, and the mixture was left
overnight at room temperature. Next day, 1 m HCl (50 ml) was added,
and the mixture was stirred for 1 h and concentrated in vacuo, the residue
was dissolved in CH2Cl2 and extracted. The organic layer was dried with
anhydrous sodium sulfate, filtered and then evaporated. The resulting
product 3 (1.4 g, 35%) was used in subsequent reactions without further
purification. HRMS, m/z: 350.1716 [M+H] (calc. for C20H24BNO2Si:
350.1742).
§
4-Benzyloxy-5-(1H-pyrrol-3-yl)pyrimidine 6. 4-Benzyloxy-5-bromo-
pyrimidine 4' (230 mg, 0.85 mmol) was dissolved in 1,2-dimethoxyethane
(20 ml) in a two-necked flask, then Pd(PPh3)4 (5 mol%) was added under
argon atmosphere, and this was stirred for 15 min. A solution of
pyrrolylboronic acid 3 (350 mg, 1 mmol) in 1,2-dimethoxyethane (20 ml)
and saturated sodium bicarbonate (10 ml) were added. The mixture was
refluxed at 90 °C for 4 h. Column chromatography on silica gel (eluent
CDCl3/MeOH, 95:5) afforded product 6 as a white powder (75 mg,
34%). 1H NMR (CDCl3) d: 8.28 (m, 1H, NH), 8.13 (s, 1H), 7.95 (s, 1H),
7.26–7.12 (m, 5H, Ph), 6.76–6.74 (m, 2H), 6.53–6.51 (m, 1H), 5.12
(s, 2H, CH2). 13C NMR (CDCl3) d: 149.44, 148.06, 146.82, 145.22,
135.30, 129.06 (2C), 128.45, 128.37, 128.27, 128.07 (2C), 120.19,
118.61, 50.08. HRMS, m/z: 252.1130 [M+H], 274.0953 [M+Na]
(calc. for C15H13N3O: 252.1131 [M+H], 274.0951 [M+Na]).
4-Acetylamino-5-(1H-pyrrol-3-yl)pyridine 7 was synthesized from
4-acetylamino-4-bromopyridine 5' in a similar manner (for details, see
Online Supplementary Materials).
Received: 6th November 2019; Com. 19/6050
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