D. Faye et al. / C. R. Chimie xxx (2017) 1e8
7
1H NMR (CDCl
NH), 7.48 (dd, J ¼ 3.2, 1.4 Hz, 1H), 7.26 (dd, J ¼ 2.4, 1.4 Hz,
, 400 MHz):
d
¼ 10.15e10.43 (br s, 1H,
1H NMR (CDCl
, 400 MHz):
d
9.89 (br s, 1H, NH), 6.84 (s,
3
3
2H), 2.85 (q, J ¼ 7.3 Hz, 4H), 1.21 (t, J ¼ 7.3 Hz, 6H) ppm.
13
1
H), 2.38 (s, 3H), 2.25 (app. tt, J ¼ 8.2, 3.9 Hz, 1H), 1.09 (app.
C NMR (CDCl
8.5 ppm.
IR (neat): n 3440, 3281, 1652, 1539, 1202, 900, 790,
3
, 100 MHz): d 192.4, 134.2, 115.2, 31.9,
dt, J ¼ 6.8, 3.4 Hz, 2H), 0.81 (app. dq, J ¼ 7.3, 3.7 Hz, 2H)
ppm.
: 1H NMR (CDCl
, 400 MHz):
d
¼ 10.15e10.43 (br s, 1H,
735 cm .
ꢀ1
4
3
NH), 7.53 (dd, J ¼ 2.4, 1.4 Hz, 1H), 7.21 (dd, J ¼ 2.4, 1.4 Hz,
HRMS (ESI): m/z calculated for C10
180.10295; found: 180.1021.
H14NO
2
[MþH]þ:
1
2
H), 3.53 (t, J ¼ 6.2 Hz, 2H, CH
2
Cl), 2.87 (t, J ¼ 7.0 Hz, 2H),
.07 (quint, J ¼ 6.7 Hz, 2H) ppm.
13
C NMR (CDCl
3
, 100 MHz): (mixture of the 3g and 4)
0
4
.20. 1,1 -(1H-Pyrrole-2,5-diyl)bis(propan-1-one) (3h)
d
¼ 195.5, 194.3, 189.0, 189.1, 132.8, 127.9, 127.8, 127.6, 127.0,
15.8, 44.8, 36.2, 26.8, 25.6, 18.1, 10.9 ppm.
IR (neat): 3284, 3094, 1638, 1554, 1382, 1271 cm
HRMS (ESI): m/z calculated for C10
78.0868; found: 178.0869.
HRMS (ESI): m/z calculated for C10
14.0635; found: 214.0637.
1
Following
the
general
procedure
from
2-
ꢀ
1
n
.
propanoylpyrrole (57 mg, 0.46 mmol), 3h was isolated as
þ
H
12NO
2
[MþH] :
a yellow foam (18 mg, 22% yield).
1
1
3
H NMR (CDCl , 400 MHz): d 9.96 (br s, 1H, NH), 7.59 (s,
H13ClNO
2
[MþH]þ:
1
H), 7.31 (s, 1H), 2.87e2.78 (m, 4H), 1.24e1.18 (m, 6H) ppm.
2
13
C NMR (CDCl
3
, 100 MHz): d 196.5, 192.5, 132.4, 127.2
(2C), 114.8, 32.9, 31.3, 8.7, 8.5 ppm.
IR (neat):
04, 800 cm
n
3264, 2976, 2937, 1644, 1552, 1378, 1182, 918,
.
4
1
.18. 1-(4-(Adamantane-1-carbonyl)-1H-pyrrol-2-yl)ethan-
-one (3g)
ꢀ
1
9
HRMS (m/z): [MþH]þ calculated for
10 2
C H14NO :
1
80.10295; found: 180.1021.
Following the general procedure from 2-acetylpyrrole
(
(
50 mg, 0.46 mmol), 3g was isolated as a yellow solid
20 mg, 15% yield).
4.21. 1-(5-Benzoyl-1H-pyrrol-2-yl)propan-1-one (2i)
1
3
H NMR (CDCl , 400 MHz): d 9.73e10.0 (br s, 1H, NH),
7
2
.69 (dd, J ¼ 3.2, 1.5 Hz, 1H), 7.39 (dd, J ¼ 2.4, 1.4 Hz, 1H),
Following the general procedure from 2-benzoylpyrrole
(79 mg, 0.46 mmol), 2i was isolated as a yellow foam
.48 (s, 3H), 2.08e2.13 (m, 3H), 2.00e2.07 (m, 3*2H), 1.75
e1.83 (m, 3*2H) ppm.
(20 mg, 19% yield).
13
1
C NMR (CDCl
31.8 (C, pyrrole), 128.6 (CH pyrrole), 124.4 (C, pyrrole),
18.0 (CH, Pyrrole), 46.4 (C, adamantyl), 39.6 (3 CH , ada-
mantyl), 36.8 (3 CH , adamantyl), 28.3 (3 CH, adamantyl),
5.6 (CH , acetyl) ppm.
IR (neat): 3314, 2901, 1655, 1637, 1548, 1388, 1360,
3
, 100 MHz):
d
201.2 (C]O), 189.0 (C]O),
3
H NMR (CDCl , 400 MHz): d 10.14 (s, 1H, NH), 7.90 (d,
1
1
J ¼ 7.8 Hz, 2H), 7.63e7.58 (m, 1H), 7.53e7.49 (m, 2H), 6.90
(d, J ¼ 4.0 Hz, 1H), 6.85 (d, J ¼ 4.0 Hz, 1H), 2.85 (q, J ¼ 7.3 Hz,
4H), 1.21 (t, J ¼ 7.3 Hz, 6H) ppm.
2
2
2
3
IR (neat): n 3266, 1663, 1626, 1547, 1375, 1279, 1209, 906,
ꢀ
1
n
891, 728 cm .
ꢀ
1
1
277, 1209 cm .
HRMS (ESI): m/z calculated for C17
H22NO
2
[MþH]þ:
4.22. 1-(4-Benzoyl-1H-pyrrol-2-yl)propan-1-one (3i)
2
72.1651; found: 272.1653.
ꢁ
Mp ¼ 197e198 C.
Following the general procedure from 2-benzoylpyrrole
Single crystals of compound 3g suitable for X-ray crys-
(
(
79 mg, 0.46 mmol), 3i was isolated as a yellow foam
tallographic analysis were obtained by slow evaporation of
chloroform solution. X-ray diffraction experiments for
monocrystals of 3g were performed at 150 K with graphite-
32 mg, 31% yield).
1
3
H NMR (CDCl , 400 MHz): d 9.95 (br s, 1H, NH), 7.98
e7.83 (d, J ¼ 7.1 Hz, 2H), 7.71 (m, 1H), 7.62 (t, J ¼ 7.1 Hz, 1H),
.52 (t, J ¼ 7.1 Hz, 2H), 7.29 (m, 1H), 2.83 (q, J ¼ 7.4 Hz, 2H),
.21 (t, J ¼ 7.4 Hz, 3H) ppm.
DEPTQ NMR (CDCl , 100 MHz):
32.6, 131.7, 128.9 (2C), 128.6 (2C), 127.5 (2C), 117.8, 32.9,
monochromatized Mo Ka radiation (
BrukereNonius Kappa CCD area detector diffractometer.
Formula C17 , formula weight 271.35, crystal system
monoclinic, space group C2/c,
b ¼ 6.4996(2) Å, c ¼ 20.3968(6) Å,
l
¼ 0.71073 Å) on a
7
1
H21NO
2
3
d 196.3, 185.2, 137.3,
a
¼
21.8308(6) Å,
1
ꢁ
b
¼ 108.2176(15) ,
8.4 ppm.
3
3
V ¼ 2749.07(14) Å , Z ¼ 8, calculated density ¼ 1.311 g/cm ,
IR (neat): n 3266, 1663, 1626, 1547, 1375, 1279, 1209, 906,
ꢀ
1
m ¼ 0.09 mm , 29,790 measured reflections, 4235 inde-
ꢀ1
.
891, 728 cm
2
2
pendent reflections, Rint ¼ 0.029, R[F > 2
s
(F )] ¼ 0.0428,
2
ꢁ
wR(F ) ¼ 0.1176, GOF ¼ 1.042, 2
q
max ¼ 60.92 , 186 pa-
4.23. 1-(4-(2,2-Dimethylpropane-1-one-1H-pyrrol-2-yl)-2,2-
rameters, final difference map between 0.387 and
dimethylpropan-1-one (3j)
ꢀ
3
ꢀ
0.217 eÅ . Program(s) used to solve structure: SHELXS-
9
7. Program(s) used to refine structure: SHELXL-2014.
Following the general procedure from 2-pivaloylpyrrole
(
76 mg, 0.5 mmol), 3j was isolated as a yellow foam (21 mg,
0
4
.19. 1,1 -(1H-Pyrrole-2,4-diyl)bis(propan-1-one) (2h)
18% yield).
1
H NMR (CDCl
3
, 400 MHz):
d
9.80 (s, 1H, NH) 7.57 (s, 1H),
201.4, 197.4, 128.9, 126.5,
Following
the
general
procedure
from
2-
7.41 (s, 1H), 1.34 (s, 18H) ppm.
13
propanoylpyrrole (57 mg, 0.46 mmol), 2h was isolated as
C NMR (CDCl
3
, 100 MHz): d
a yellow foam (18 mg, 22% yield).
124.2, 116.8, 43.7, 43, 28.1 ppm.
Please cite this article in press as: D. Faye, et al., Zinc mediated straightforward access to diacylpyrroles, Comptes Rendus Chimie
2017), http://dx.doi.org/10.1016/j.crci.2017.01.003
(