The Journal of Organic Chemistry
NOTE
90/10). Mp: 82ꢀ83 °C. 1H NMR (500 MHz, CDCl3): δ 7.16 (d, J = 7.9
Hz, 1H), 7.03 (s, 1H), 6.83 (d, J = 7.9 Hz, 1H), 3.88 (s, 3H), 2.25ꢀ2.20
(m, 1H), 1.04ꢀ1.00 (m, 2H), 0.71ꢀ0.68 (m, 2H). 13C NMR (125
MHz, CDCl3): δ 158.3, 138.9, 125.1, 125.0, 119.4, 112.9, 109.4, 55.9,
9.7, 9.1. FT-IR (neat): 2224, 1508, 1266, 1036 cmꢀ1. HRMS (ESI): m/z
calcd for C11H11NO (M)+ 173.0841, found 173.0843.
FT-IR (neat): 2226, 1626 cmꢀ1. HRMS (ESI): m/z calcd for C14H12N
(M + H)+ 194.0970, found 194.0973.
Procedure B: 6-Cyclopropylquinoline (3a). A Biotage micro-
wave vial was charged with PdCl2(COD) (1.4 mg, 5.0 μmol), RuPhos
(4.7 mg, 10 μmol), quinolin-6-yl methanesulfonate (55.8mg, 0.25 mmol),
cyclopropyl trifluoroborate (47.2 mg, 0.33 mmol), and K3PO4 (382 mg,
1.80 mmol). The test tube was sealed with a cap lined with a disposable
Teflon septum, evacuated under vacuum, and purged with argon three
times. A t-BuOH/H2O mixture (1.25 mL/1.25 mL) was added under
argon. The reaction mixture was heated to 110 °C for 16 h before
cooling to room temperature. The reaction mixture was extracted with
EtOAc (3 ꢁ 2 mL) and then dried (MgSO4). The solvent was removed
in vacuo, and the crude product was purified by preparative silica gel
chromatography (elution with hexanes/EtOAc 80/20) to give 3a in 94%
yield (39.6 mg) as a colorless oil. 1H NMR (500 MHz, CDCl3): δ 8.81
(s, 1H), 8.03 (d, J = 8.1 Hz, 1H), 7.98 (d, J = 8.8 Hz, 1H), 7.46 (s, 1H),
7.40 (d, J = 8.8 Hz, 1H), 7.33ꢀ7.31 (m, 1H), 2.08ꢀ2.05 (m, 1H),
1.06ꢀ1.04 (m, 2H), 0.81ꢀ0.80 (m, 2H). 13C NMR (125 MHz, CDCl3):
δ 149.3, 147.0, 142.3, 135.2, 129.2, 128.2, 128.1, 123.3, 121.0, 15.4, 9.4.
FT-IR (neat): 1592, 1499 cmꢀ1. HRMS (ESI): m/z calcd for C12H12N
(M + H)+ 170.0970, found 170.0975.
5-Cyclopropyl-2-methylbenzo[d]thiazole (3b). Following
procedure B, the reaction was carried out with 2-methylbenzo[d]thiazol-
5-yl methanesulfonate (60.8 mg, 0.25 mmol) to give 3b (40.3 mg, 85%)
as a yellow oil after silica gel chromatography (elution with hexanes/
EtOAc 95/5). 1H NMR (500 MHz, CDCl3): δ 7.65 (d, J = 8.3 Hz, 1H),
7.63 (d, J = 1.5 Hz, 1H), 7.09 (dd, J = 8.3, 1.5 Hz, 1H), 2.80 (s, 3H),
2.04ꢀ1.99 (m, 1H), 1.02ꢀ0.98 (m, 2H), 0.77ꢀ0.73 (m, 2H). 13C NMR
(125 MHz, CDCl3): δ 167.0, 153.8, 142.3, 132.4, 123.3, 120.8, 118.9,
20.0, 15.3, 9.4. FT-IR (neat): 1525 cmꢀ1. HRMS (ESI): m/z calcd for
C11H12NS (M + H)+ 190.0690, found 190.0695.
4-Cyclopropyldibenzo[b,d]thiophene (3c). Following proce-
dure B, the reaction was carried out with dibenzo[b,d]furan-4-yl
methanesulfonate (69.5 mg, 0.25 mmol) to give 3c (49.7 mg, 89%) as
a colorless oil after silica gel chromatography (elution with hexanes/
EtOAc 95/5). 1H NMR (500 MHz, CDCl3): δ 8.17ꢀ8.14 (m, 1H), 8.00
(d, J = 7.7 Hz, 1H), 7.91ꢀ7.89 (m, 1H), 7.48ꢀ7.45 (m, 2H), 7.42ꢀ7.39
(m, 1H), 7.13 (d, J = 7.3 Hz, 1H), 2.18ꢀ2.12 (m, 1H), 1.12ꢀ1.08 (m,
2H), 0.89ꢀ0.86 (m, 2H). 13C NMR (125 MHz, CDCl3): δ 140.8, 139.6,
137.7, 136.3, 135.5, 126.7, 124.9, 124.4, 123.2, 122.9, 121.9, 119.3, 15.0,
7.3. FT-IR (neat): 1442 cmꢀ1. HRMS (ESI): m/z calcd for C15H12S
(M)+ 224.0660, found 224.0662.
8-Cyclopropylquinoline (3d). Following procedure B, the reac-
tion was carried out with quinolin-8-yl methanesulfonate (55.8 mg, 0.25
mmol) to give 3d (19.3 mg, 46%) as a red oil after preparative silica gel
chromatography (elution with hexanes/EtOAc 80/20). 1H NMR (500
MHz, CDCl3): δ 8.99 (dd, J = 3.9, 1.4 Hz, 1H), 8.15 (dd, J = 8.2, 1.4 Hz,
1H), 7.63 (d, J = 8.2 Hz, 1H), 7.47ꢀ7.40 (m, 2H), 7.20 (d, J = 7.0 Hz,
1H), 3.22ꢀ3.16 (m, 1H), 1.20ꢀ1.18 (m, 2H), 0.87ꢀ0.85 (m, 2H). 13C
NMR (125 MHz, CDCl3): δ 149.5, 147.7, 142.7, 136.6, 128.4, 126.5,
125.2, 123.2, 121.1, 10.7, 9.6. FT-IR (neat): 1498 cmꢀ1. HRMS (ESI):
m/z calcd for C12H12N (M + H)+ 170.0970, found 170.0977.
4-Cyclopropyl-1,10-biphenyl (2f). Following procedure A, the
reaction was carried out with [1,10-biphenyl]-4-yl methanesulfonate
(124mg, 0.50mmol), Pd(OAc)2 (5.6mg, 25μmol), and RuPhos (23.3 mg,
50.0 μmol) to give 2f (40.4 mg, 42%) as a white solid after silica gel
1
chromatography (elution with petroleum ether). Mp: 68ꢀ71 °C. H
NMR (500 MHz, CDCl3): δ 7.62 (d, J = 7.3 Hz, 2H), 7.52 (d, J = 8.3 Hz,
2H), 7.47ꢀ7.45 (m, 2H), 7.44ꢀ7.34 (m, 1H), 7.18 (d, J = 8.3 Hz, 2H),
2.00ꢀ1.94 (m, 1H), 1.05ꢀ1.01 (m, 2H), 0.79ꢀ0.77 (m, 2H). 13C NMR
(125 MHz, CDCl3): δ 143.4, 141.3, 138.5, 128.9, 127.2, 127.1, 126.2,
15.3, 9.5. FT-IR (neat): 1488 cmꢀ1. HRMS (ESI) m/z calcd. for C15H15
(M + H)+ 195.1174, found 195.1176.
4-Cyclopropylphenylmethanone (2g). Following procedure
A, the reaction was carried out with 4-benzoylphenyl methanesulfonate
(69.0 mg, 0.25 mmol) to give 2g (31.1 mg, 56%) as an off-white solid
after preparative silica gel chromatography (elution with hexanes/
1
EtOAc 95/5). Mp: 60ꢀ62 °C. H NMR (500 MHz, CDCl3): δ 7.77
(d, J = 7.7 Hz, 2H), 7.71 (d, J = 7.9 Hz, 2H), 7.58ꢀ7.55 (m, 1H),
7.48ꢀ7.45 (m, 2H), 7.14 (d, J = 7.9 Hz, 2H), 1.99ꢀ1.94 (m, 1H),
1.08ꢀ1.06 (m, 2H), 0.80ꢀ0.79 (m, 2H). 13C NMR (125 MHz, CDCl3):
δ 196.5, 149.9, 138.2, 134.8, 132.3, 130.6, 130.0, 128.3, 125.4, 15.9, 10.5.
FT-IR (neat): 1648, 1605 cmꢀ1. HRMS (ESI): m/z calcd for C16H15O
(M + H)+ 223.1123, found 223.1129.
1-Cyclopropyl-4-methoxynaphthalene (2h). Following pro-
cedure A, the reaction was carried out with 4-methoxynaphthalen-1-yl
methanesulfonate (63.0 mg, 0.25 mmol), Pd(OAc)2 (2.8 mg, 12 μmol),
and RuPhos (11.7 mg, 25.0 μmol) to give 2h (44.5 mg, 90%) as a
colorless oil after preparative silica gel chromatography (elution with
petroleum ether/hexanes/EtOAc 68/30/2). 1H NMR (500 MHz,
CDCl3): δ 8.41 (d, J = 8.3 Hz, 1H), 8.34 (d, J = 8.3 Hz, 1H),
7.63ꢀ7.60 (m, 1H), 7.56ꢀ7.53 (m, 1H), 7.23 (d, J = 7.9 Hz, 1H),
6.74 (d, J = 7.9 Hz, 1H), 4.00 (s, 3H), 2.30ꢀ2.25 (m, 1H), 1.06ꢀ1.04
(m, 2H), 0.76ꢀ0.74 (m, 2H). 13C NMR (125 MHz, CDCl3): δ 154.4,
134.5, 131.3, 126.4, 125.8, 125.2, 124.5, 124.3, 122.5, 103.3, 55.6, 13.1,
6.2. FT-IR (neat): 1588, 1271, 1098 cmꢀ1. HRMS (ESI): m/z calcd for
C14H14O (M)+. 198.1045, found 198.1047.
Methyl 6-Cyclopropyl-2-naphthoate (2i). Following proce-
dure A, the reaction was carried out with methyl 6-((methylsulfonyl)-
oxy)-2-naphthoate (70.0 mg, 0.25 mmol), Pd(OAc)2 (2.8 mg, 12 μmol),
and RuPhos (11.7 mg, 25.0 μmol) to give 2i (24.7 mg, 44%) as a
colorless oil after preparative silica gel chromatography (elution with
hexanes/EtOAc 98/2). 1H NMR (500 MHz, CDCl3): δ 8.55 (s, 1H),
8.01 (d, J = 8.5 Hz, 1H), 7.83 (d, J = 8.5 Hz, 1H), 7.76 (d, J = 8.5 Hz, 1H),
7.55 (s, 1H), 7.23 (d, J = 8.5 Hz, 1H), 3.97 (s, 3H), 2.10ꢀ2.05 (m, 1H),
1.10ꢀ1.06 (m, 2H), 0.86ꢀ0.83 (m, 2H). 13C NMR (125 MHz,
CDCl3): δ 167.5, 144.7, 135.9, 131.0, 131.0, 129.5, 127.5, 126.5,
125.6, 125.4, 123.7, 52.3, 16.0, 9.9. FT-IR (neat): 1706, 1292, 1209 cmꢀ1
.
HRMS (ESI): m/z calcd for C15H14O2 (M + H)+ 227.1072, found
227.1075.
4-Cyclopropyldibenzo[b,d]furan (3e). Following procedure B,
the reaction was carried out with dibenzo[b,d]furan-4-yl methanesulfo-
nate (65.5 mg, 0.25 mmol), PdCl2(COD) (3.6 mg, 12 μmol), and
RuPhos (11.8 mg, 25.0 μmol) to give 3e (47.0 mg, 72%) as a colorless oil
after preparative silica gel chromatography (elution with pentane). 1H
NMR (500 MHz, CDCl3): δ 7.96 (d, J = 7.7 Hz, 1H), 7.76 (dd, J = 7.7,
0.9 Hz, 1H), 7.62 (d, J = 8.3 Hz, 1H), 7.49ꢀ7.47 (m, 1H), 7.37ꢀ7.35
(m, 1H), 7.28ꢀ7.25 (m, 1H), 7.04 (d, J = 7.7 Hz, 1H), 2.48ꢀ2.42 (m,
1H), 1.15ꢀ1.11 (m, 2H), 1.01ꢀ0.98 (m, 2H). 13C NMR (125 MHz,
CDCl3): δ 156.2, 155.3, 128.2, 127.1, 124.7, 123.8, 123.1, 123.0, 122.7,
6-Cyclopropyl-2-naphthonitrile (2j). Following procedure A,
the reaction was carried out with 6-cyanonaphthalen-2-yl methanesul-
fonate (61.8 mg, 0.25 mmol), Pd(OAc)2 (2.8 mg, 12 μmol), and RuPhos
(11.7 mg, 25.0 μmol) to give 2j (28.0 mg, 58%) as a white solid after
preparative silica gel chromatography (elution with hexanes/EtOAc 90/
10). Mp: 103ꢀ104 °C. 1H NMR (500 MHz, CDCl3): δ 8.15 (s, 1H),
7.79 (d, J = 8.6 Hz, 1H), 7.76 (d, J = 8.6 Hz, 1H), 7.56ꢀ7.54 (m, 2H),
7.28 (dd, J = 8.6, 1.7 Hz, 1H), 2.11ꢀ2.05 (m, 1H), 1.12ꢀ1.10 (m, 2H),
0.86ꢀ0.85 (m, 2H). 13C NMR (125 MHz, CDCl3): δ 145.6, 134.8,
133.8, 130.5, 128.3, 128.3, 126.5, 126.2, 123.7, 119.4, 108.0, 15.8, 9.9.
120.9, 117.6, 111.8, 10.3, 8.2. FT-IR (neat): 1450, 1186, 1068 cmꢀ1
HRMS (ESI): m/z calcd for C15H12O (M)+ 208.0888, found 208.0886.
.
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dx.doi.org/10.1021/jo2015246 |J. Org. Chem. 2011, 76, 8126–8130