Abstract
A series of tetrasubstituted 3-alkynylpyrroles were synthesized
via a three-component reaction of imines, phenylacetylene, and dialkylzinc.
This method provided a new strategy for preparing tetrasubstituted
3-alkynylpyrroles which can be converted into more complex molecules.
Key words
multicomponent reactions - pyrroles - tetrasubstituted
3-alkynylpyrroles
References and Notes
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General Procedure
for the Preparation of Imines
To a round-bottomed
flask containing the amine (10 mmol) in toluene (20 mL) was added
anhyd Na2 SO4 (50 mmol). The mixture was stirred,
and then ethyl glyoxalate (12 mmol) was added slowly. After the
reaction was completed (about 1 h, monitored by TLC), Na2 SO4 was
removed by filtration, and toluene was distilled under reduced pressure
to yield the crude imine (95% yield), which was used for
the next step without purification.General
Procedure for the Preparation of Pyrrole Derivatives
2 Zn in toluene (6 mmol) was added at r.t. The resulting
solution was stirred for 1 h, and then the imine 2 O (5 mL). The
mixture was diluted with Et2 O, stirred for 5 min, and
then filtered through Celite. The collected filtrate was separated,
and the aqueous phase was extracted with Et2 O (3 × 3
mL). The combined organic phases were washed with brine and dried
over Na2 SO4 . After removal of the solvent
under reduced pressure, the crude product was purified by flash
column chromatography (eluent: EtOAc-PE, 1:50) to afford
the desired pyrrole products.2-Methyl-5-phenyl-3-(phenylethynyl)-1-
p
-tolyl-1
H
-pyrrole (1a)
White solid. ¹ H
NMR (300 MHz, CDCl3 ): δ = 2.34 (s,
3 H), 2.43 (s, 3 H), 6.60 (s, 1 H), 7.07-7.10 (d, 2 H),
7.16-7.19 (m, 7 H), 7.32-7.41 (m, 3 H), 7.57-7.60
(d, 2 H). ¹³ C NMR (75 MHz, CDCl3 ): δ = 12.75,
21.63, 85.48, 90.72, 103.35, 111.27, 124.78, 126.47, 127.56, 128.28,
128.50, 130.02, 131.47, 132.93, 134.07, 136.40, 136.51, 137.97.
HRMS: m/z calcd for
C26 H21 N [M+ ]:
347.1679; found: 347.1680.
