4H), 2.34 (t, J = 8.8 Hz, 1H), 1.74 (d, J = 10.2 Hz, 2H), 1.70 –
1H), 7.63 (t, J = 7.3 Hz, 1H), 7.52 (t, J = 7.6 Hz, 2H), 7.30 (dd, J
= 7.5, 4.9 Hz, 1H), 3.43 (t, J = 7.4 Hz, 2H), 2.95 (t, J = 7.3 Hz,
2H).13C NMR (151 MHz, DMSO-d6, ppm): δ 199.10, 149.94,
147.34, 136.86, 136.68, 136.10, 133.38, 128.89, 128.10, 123.51,
39.13 26.72.
ACCEPTED MANUSCRIPT
1.63 (m, 2H), 1.58 (d, J = 11.7 Hz, 1H), 1.27 – 1.09 (m, 5H). 13C
NMR (151 MHz, DMSO-d6, ppm): δ 212.34, 141.49, 128.35,
125.90, 49.77, 41.44, 29.24, 28.05, 25.64, 25.27.
4.4.14. 4,4-dimethyl-1-phenylpentan-3-one (3na).5d Yellow oil.
1H NMR (400 MHz, DMSO-d6, ppm): δ 7.25 (t, J = 7.3 Hz, 2H),
7.20 (d, J = 7.2 Hz, 2H), 7.16 (t, J = 7.1 Hz, 1H), 2.84 (t, J = 7.0
Hz, 2H), 2.74 (t, J = 7.0 Hz, 2H), 1.03 (s, 9H). 13C NMR (151
MHz, DMSO-d6, ppm): δ 214.25, 141.59, 128.45, 128.34, 125.92,
43.57, 37.71, 29.60, 26.12.
4.4.23.
1-phenyl-3-(thiophen-2-yl)propan-1-one
(3aj).4e
1
Yellow oil. H NMR (400 MHz, CDCl3): δ 7.97 (d, J = 7.6 Hz,
2H), 7.57 (t, J = 7.3 Hz, 1H), 7.46 (t, J = 7.6 Hz, 2H), 7.13 (d, J =
4.9 Hz, 1H), 6.97 – 6.89 (m, 1H), 6.87 (s, 1H), 3.40 – 3.35 (m,
2H), 3.33 – 3.27 (m, 2H). 13C NMR (101 MHz, DMSO-d6, ppm):
δ 198.80, 143.87, 136.69, 133.40, 128.90, 128.11, 127.02, 124.94,
123.84, 39.82, 23.77.
4.4.15.1-phenyl-3-(o-tolyl)propan-1-one (3ab).5a Colorless oil.
1H NMR (400 MHz, DMSO-d6, ppm): δ 7.99 (d, J = 7.6 Hz, 2H),
7.63 (t, J = 7.3 Hz, 1H), 7.52 (t, J = 7.5 Hz, 2H), 7.19 (d, J = 5.9
Hz, 1H), 7.16 – 7.05 (m, 3H), 3.31 (t, J = 7.6 Hz, 2H), 2.91 (t, J =
7.5 Hz, 2H), 2.28 (s, 3H). 13C NMR (151 MHz, DMSO-d6, ppm):
δ 199.40, 139.46, 136.75, 135.85, 133.29, 130.10, 128.86, 128.69,
128.12, 126.12, 126.05, 38.47, 26.99, 19.15.
4.4.24. 3-(furan-2-yl)-1-phenylpropan-1-one (3ak).5d Yellow
1
oil. H NMR (400 MHz, DMSO-d6, ppm): δ 8.00 (d, J = 7.6 Hz,
2H), 7.64 (t, J = 7.2 Hz, 1H), 7.58 – 7.42 (m, 3H), 6.34 (s, 1H),
6.14 (s, 1H), 3.37 (d, J = 7.5 Hz, 2H), 2.96 (t, J = 7.3 Hz, 2H).
13C NMR (101 MHz, DMSO-d6, ppm): δ 198.70, 154.83, 141.44,
136.64, 133.39, 128.89, 128.11, 110.56, 105.41, 36.30, 22.11.
4.4.25. 3-(naphthalen-2-yl)-1-phenylpropan-1-one (3al).4d
White solid. 1H NMR (400 MHz, DMSO-d6, ppm): δ 8.00 (d, J =
7.6 Hz, 2H), 7.83 (t, J = 8.8 Hz, 3H), 7.76 (s, 1H), 7.61 (s, 1H),
7.54 – 7.39 (m, 5H), 3.44 (d, J = 8.8 Hz, 2H), 3.12 (t, J = 7.4 Hz,
2H). 13C NMR (101 MHz, DMSO-d6, ppm): δ 199.09, 138.90,
136.59, 133.13, 131.61, 128.69, 127.93, 127.67, 127.43, 127.26
126.18, 125.95, 125.22, 39.30, 29.62.
4.4.16. 1-phenyl-3-(p-tolyl)propan-1-one (3ac).5d Colorless oil.
1H NMR (400 MHz, DMSO-d6, ppm): δ 7.97 (d, J = 7.6 Hz, 2H),
7.62 (t, J = 7.3 Hz, 1H), 7.51 (t, J = 7.5 Hz, 2H), 7.15 (d, J = 7.7
Hz, 2H), 7.07 (d, J = 7.7 Hz, 2H), 3.32 (t, J = 7.5 Hz, 2H), 2.89 (t,
J = 7.4 Hz, 2H), 2.24 (s, 3H). 13C NMR (151 MHz, DMSO-d6,
ppm): δ 199.35, 138.26, 136.79, 134.91, 133.27, 128.99, 128.87,
128.41, 128.07, 39.76, 29.26, 20.78.
4.4.17. 3-(2-methoxyphenyl)-1-phenylpropan-1-one (3ad).4e
White solid. 1H NMR (400 MHz, DMSO-d6, ppm): δ 7.97 (d, J =
7.6 Hz, 2H), 7.62 (t, J = 7.3 Hz, 1H), 7.51 (t, J = 7.5 Hz, 2H),
7.18 (t, J = 7.4 Hz, 2H), 6.94 (d, J = 8.2 Hz, 1H), 6.86 (t, J = 7.3
Hz, 1H), 3.78 (s, 3H), 3.26 (t, J = 7.6 Hz, 2H), 2.90 (t, J = 7.5 Hz,
2H). 13C NMR (101 MHz, DMSO-d6, ppm): δ 199.56, 157.28,
136.73, 133.24, 129.79, 128.97, 128.86, 128.06, 127.56, 120.40,
110.68, 55.36, 38.28, 24.87.
4.4.18. 3-(3-methoxyphenyl)-1-phenylpropan-1-one (3ae).4e
White solid. 1H NMR (400 MHz, DMSO-d6, ppm): δ 7.99 (d, J =
7.6 Hz, 2H), 7.63 (t, J = 7.3 Hz, 1H), 7.52 (t, J = 7.5 Hz, 2H),
7.18 (t, J = 7.8 Hz, 1H), 6.85 (d, J = 7.9 Hz, 2H), 6.74 (d, J = 7.6
Hz, 1H), 3.72 (s, 3H), 3.38 (d, J = 7.4 Hz, 2H), 2.91 (t, J = 7.4 Hz,
2H). 13C NMR (101 MHz, DMSO-d6, ppm): δ 199.34, 159.46,
143.01, 136.79, 133.30, 129.43, 128.88, 128.11, 120.80, 114.27,
111.48, 55.06, 39.58, 29.71.
1
4.4.26. 1-phenylhexan-1-one (3am).5d Colorless oil. H NMR
(400 MHz, DMSO-d6, ppm): δ 7.96 (d, J = 7.6 Hz, 2H), 7.62 (t, J
= 7.3 Hz, 1H), 7.52 (t, J = 7.6 Hz, 2H), 3.00 (t, J = 7.2 Hz, 2H),
1.67 – 1.54 (m, 2H), 1.36 – 1.25 (m, 4H), 0.87 (t, J = 6.4 Hz,
3H).13C NMR (151 MHz, DMSO-d6, ppm): δ 200.16, 136.89,
133.12, 128.81, 127.99, 37.99, 31.03, 23.67, 22.17, 13.99.
4.5. Hydrogen transfer between α,β-unsaturated ketone and
benzylic alcohol.
Cs2CO3 (0.6 mmol, 195.6 mg) and toluene (1 mL) were placed in
a Schlenk tube under a N2 atmosphere. [RuCl2(η6-p-cymene)]2
(0.005 mmol, 3.1 mg), L1 (0.01mmol, 2.8 mg), 2a (1.1 mmol,
119.6 mg) and 1a (1.0 mmol, 120 mg) were added in that order
and the Schlenk tube was then closed and stirred at 120 oC for 18
h. The reaction was cooled to room temperature. 1,3,5-
Trimethoxybenzene (168 mg, 1.0 mmol, internal standard) was
added and the mixture was then diluted with ethyl acetate (18
mL). An aliquot of the reaction solution was further analyzed by
1H NMR spectroscopy.
4.4.19. 3-(4-methoxyphenyl)-1-phenylpropan-1-one (3af).4e
1
White solid. H NMR (400 MHz, DMSO-d6, ppm): δ 7.97 (d, J =
7.6 Hz, 2H), 7.62 (t, J = 7.2 Hz, 1H), 7.51 (t, J = 7.5 Hz, 2H),
7.18 (d, J = 8.3 Hz, 2H), 6.83 (d, J = 8.4 Hz, 2H), 3.70 (s, 3H),
3.31 (d, J = 7.4 Hz, 2H), 2.88 (t, J = 7.4 Hz, 2H). 13C NMR (101
MHz, DMSO-d6, ppm): δ 199.43, 157.68, 136.81, 133.27, 133.23,
129.50, 128.87, 128.08, 113.85, 55.14, 39.97, 28.83.
1
4.6. In situ monitoring of the ruthenium hybrid by H NMR
and ESI-MS.
4.4.20. 3-(4-bromophenyl)-1-phenylpropan-1-one (3ag).5d
Cs2CO3 (0.6 mmol, 195.6 mg) and toluene-d8 (1 mL) were
placed in a Schlenk tube under a N2 atmosphere. [RuCl2(η6-p-
cymene)]2 (0.025 mmol, 15.5 mg), L1 (0.05 mmol, 14.0 mg), 2a
(1.1 mmol, 120 mg) and 1a (1.0 mmol, 120 mg) were added in
1
White solid. H NMR (400 MHz, DMSO-d6, ppm): δ 7.98 (d, J =
7.6 Hz, 2H), 7.62 (d, J = 7.3 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H),
7.46 (d, J = 8.2 Hz, 2H), 7.26 (d, J = 8.1 Hz, 2H), 3.38 (t, J = 7.4
Hz, 2H), 2.92 (t, J = 7.4 Hz, 2H). 13C NMR (101 MHz, DMSO-d6)
δ 199.11, 140.92, 136.71, 133.34, 131.22, 130.91, 128.88, 128.09,
119.05, 39.31, 28.94.
o
that order and the Schlenk tube was closed and stirred at 120 C
for a required time. The reaction was cooled to room temperature
and 0.5 mL of the reaction solution was transferred into an NMR
tube under a N2 atmosphere for the 1H NMR analysis. An aliquot
of the reaction solution was diluted by methanol and analyzed by
ESI-MS.
4.4.21. 3-(4-chlorophenyl)-1-phenylpropan-1-one (3ah).5d
White solid. 1H NMR (400 MHz, DMSO-d6, ppm): δ 7.98 (d, J =
7.5 Hz, 2H), 7.62 (d, J = 7.3 Hz, 1H), 7.52 (t, J = 7.6 Hz, 2H),
7.32 (s, 4H), 3.38 (t, J = 7.4 Hz, 2H), 2.93 (t, J = 7.4 Hz, 2H). 13
C
Acknowledgments
NMR (101 MHz, DMSO-d6, ppm): δ 199.13, 140.48, 136.72,
133.34, 130.64, 130.49, 128.88, 128.31, 128.09, 39.39, 28.89.
The authors thank the National Natural Science Foundation of
China (21271134, 21373142, 21531006 and 21671144) and State
Key Laboratory of Organometallic Chemistry, Shanghai Institute
of Organic Chemistry, Chinese Academy of Sciences (2015kf-
4.4.22. 1-phenyl-3-(pyridin-3-yl)propan-1-one (3ai).4e White
solid. 1H NMR (400 MHz, DMSO-d6, ppm): δ 8.52 (s, 1H), 8.39
(d, J = 4.2 Hz, 1H), 7.99 (d, J = 7.6 Hz, 2H), 7.71 (d, J = 7.7 Hz,
8