A simple and direct method for the palladium-catalyzed oxidative coupling of unactivated allylarenes with classic arenes

Article abstract of DOI:10.1002/cctc.201402075

An efficient route to engineer vinylarene structures by the Pd ^II-catalyzed oxidative coupling of unactivated allylarenes with classic arenes was developed. The methodology features the use of unactivated allylarenes with no prefunctionalization and classic arenes without installed directing groups. A variety of vinylarenes and their saturated derivatives were obtained. They make a great couple: An efficient route to engineer vinylarene structures by Pd^II-catalyzed oxidative coupling of unactivated allylarenes with classic arenes is developed. The methodology features the use of unactivated allylarenes with no prefunctionalization and classic arenes without installed directing groups. A variety of vinylarenes and their saturated derivatives are obtained.

Full text of DOI:10.1002/cctc.201402075

Supporting Information
ꢀ Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2014
A Simple and Direct Method for the Palladium-Catalyzed
Oxidative Coupling of Unactivated Allylarenes with Classic
Arenes
Weiwei Jin, Wing-Tak Wong,* and Ga-Lai Law*[a]
cctc_201402075_sm_miscellaneous_information.pdf

Experimental procedures and analytical data
Contents:
1. General consideration
2
2. Experimental procedures
3
3. Intermolecular competition experiment
4. Kinetic isotopic effect study
5. Analytical data
4
5
6
6. The crystal structure of (E)-3i
7. Copies of 1H, 13C and 19F NMR spectra
3
1 4
1

1. General consideration
1H and 13C NMR spectra were recorded on a Bruker DPX400 NMR spectrometer,
the chemical shift values are refered to TMS = 0.00 ppm and solvent residues of CDCl3
19
are ((1H), 7.26 ppm and (13C), 77.16 ppm). F NMR was recorded on a Bruker
DPX400 NMR spectrometer (CFCl3 as outside standard and positive low field ).
Chemical shifts (δ) are reported in ppm; coupling constants (J) are reported in Hz.
Standard abbreviations are used: s = singlet, d = doublet, t = triplet, q = quartet, m =
multiplet. HRMS analysis was carried out on a Waters-Micromass GCT permier mass
spectrometer operated in electron ionization mode. X-ray crystallographic study was
performed by a Bruker CCD area detector diffractometer. Analytical TLC plates,
Merck KGaA silica gel 60F254 were viewed by UV light (254 nm). Column
chromatographic purification was performed on SDZF silica gel 160.
All the chemical reagents were purchased from commercial sources and used as
received unless otherwise indicated. Benzene, toluene, o-xylene, m-xylene and
p-xylene were freshly distilled from sodium/benzophenone and stored over 4A
molecular sieve.
2

2. Experimental procedures
2.1. A typical procedure for the direct oxidative coupling of unactivated
allylarenes 1 with classic arenes 2-Synthesis of (E)-prop-1-ene-1,3-diyldibenzene
(3a): A mixture of 1a (59 mg, 0.5 mmol), Pd(TFA)2 (17 mg, 0.05 mmol), AgOAc (125
mg, 0.75 mmol) and PivOH (204 mg, 2 mmol) in benzene 2a (3 mL) was stirred at 80
oC for 12 h. After cooling to ambient temperature, the resultant mixture was filtered
through a short pad of celite and rinsed with 10 mL DCM. The organic phase was
removed under reduced pressure. The resultant residue was purified by silica gel
o
column chromatography (eluent: petroleum ether (35-60 C)) to afford 3a as a
colorless liquid (58 mg, 60%).
2.2. A typical procedure for the hydrogenation of 3/3′-Synthesis of
1-methyl-4-(3-phenylpropyl)benzene (3d′′): The mixture of 3d/3d′ (40 mg, 0.19 mmol)
was dissolved in EtOH (5 mL), and a catalytic amount of Pd/C (5 mg, 10 mol%) was
added. The air in the flask was exchanged to hydrogen, using a pump and a hydrogen
balloon, repeated thrice. Another hydrogen balloon was connected to the flask and the
mixture was stirred vigorously for 12 hours. After the reaction had finished, the crude
mixture was filtered, concentrated in vacuo and purified by silica gel column
chromatography (eluent: petroleum ether (35-60 oC)) to afford 3d′′ as a colorless liquid
(36 mg, 90%). 3f′′ was obtained in 94% yield under the same method.
2.3. A typical procedure for the direct oxidative coupling of homoallylbenzene 1j
with benzene 2a-Synthesis of (E)-but-1-ene-1,4-diyldibenzenee (3j): A mixture of 1j
(66 mg, 0.5 mmol), Pd(TFA)2 (17 mg, 0.05 mmol), AgOAc (125 mg, 0.75 mmol) and
o
PivOH (204 mg, 2 mmol) in benzene 2a (3 mL) was stirred at 80 C for 12 h. After
cooling to ambient temperature, the resultant mixture was filtered through a short pad
of celite and rinsed with 10 mL DCM. The organic phase was removed under reduced
pressure. The resultant residue was purified by silica gel column chromatography
(eluent: petroleum ether (35-60 oC)) to afford 3j as a colorless liquid (54 mg, 52%).
3

2.4. A typical procedure for the control experiment
A mixture of 5c (63 mg, 0.32 mmol), Pd(TFA)2 (11 mg, 0.032 mmol), AgOAc (80
mg, 0.48 mmol) and PivOH (131 mg, 1.28 mmol) in benzene (2 mL) was stirred at 80
oC for 40 h. After cooling to ambient temperature, the resultant mixture was filtered
through a short pad of celite and rinsed with 10 mL DCM. The organic phase was
removed under reduced pressure. The resultant residue was purified by silica gel
o
column chromatography (eluent: petroleum ether (35-60 C)) to afford 3a as a
colorless liquid (3 mg, 5%).
3. Intermolecular competition experiment
A mixture of 1a (30 mg, 0.25 mmol), 1e (37 mg, 0.25 mmol), Pd(TFA)2 (17 mg, 0.05
mmol), AgOAc (125 mg, 0.75 mmol) and PivOH (204 mg, 2.0 mmol) in benzene (3.0
o
mL) was stirred at 80 C for 12 h. After cooling to ambient temperature, the resultant
mixture was filtered through a short pad of celite and rinsed with 10 mL DCM. The
organic phase was removed under reduced pressure. The resultant residue was purified
by silica gel column chromatography (eluent: petroleum ether (35-60 oC)) to afford 3a
(24 mg, 48%) and 3e/3e′ (32 mg, 57%).
4

A mixture of 1e (37 mg, 0.25 mmol), 1g (52 mg, 0.25 mmol), Pd(TFA)2 (17 mg, 0.05
mmol), AgOAc (125 mg, 0.75 mmol) and PivOH (204 mg, 2.0 mmol) in benzene (3.0
o
mL) was stirred at 80 C for 12 h. After cooling to ambient temperature, the resultant
mixture was filtered through a short pad of celite and rinsed with 10 mL DCM. The
organic phase was removed under reduced pressure. The resultant residue was purified
o
by silica gel column chromatography (eluent: petroleum ether (35-60 C)) to afford
3e/3e′ (36 mg, 65%) and 3g (37 mg, 52%).
A mixture of 1a (59 mg, 0.5 mmol), Pd(TFA)2 (17 mg, 0.05 mmol), AgOAc (125
mg, 0.75 mmol) and PivOH (204 mg, 2.0 mmol) in anisole (1.5 mL)/fluorobenzene
o
(1.5 mL) was stirred at 80 C for 12 h. After cooling to ambient temperature, the
resultant mixture was filtered through a short pad of celite and rinsed with 10 mL
DCM. The organic phase was removed under reduced pressure. The resultant residue
was purified by silica gel column chromatography (eluent: petroleum ether (35-60 oC))
to afford 4i (34 mg, 30%) and 4j (14 mg, 13%).
5

4. Kinetic isotopic effect study
A mixture of 1a (64 mg, 0.54 mmol), Pd(TFA)2 (18 mg, 0.054 mmol), AgOAc (135
mg, 0.81 mmol) and PivOH (221 mg, 2.16 mmol) in benzene-d6 (3 mL) was stirred at
80 oC for 12 h. After cooling to ambient temperature, the resultant mixture was filtered
through a short pad of celite and rinsed with 10 mL DCM. The organic phase was
removed under reduced pressure. The resultant residue was purified by silica gel
o
column chromatography (eluent: petroleum ether (35-60 C)) to afford 3a-d5 as a
colorless liquid (18 mg, 17%).
A mixture of 1i (96 mg, 0.57 mmol), Pd(TFA)2 (19 mg, 0.057 mmol), AgOAc (143
mg, 0.85 mmol) and PivOH (233 mg, 2.3 mmol) in toluene-d8 (3 mL) was stirred at 80
oC for 12 h. After cooling to ambient temperature, the resultant mixture was filtered
through a short pad of celite and rinsed with 10 mL DCM. The organic phase was
removed under reduced pressure. The resultant residue was purified by silica gel
o
column chromatography (eluent: petroleum ether (35-60 C)) to afford 4i-d7 as a
colorless liquid (27 mg, 18%).
6

5. Analytical data
3a
3a Colorless liquid. 1H NMR (CDCl3, 400 MHz) 7.47-7.28m, 10 H, 6.56 (d,
J = 15.8 Hz, 1 H), 6.46 (dt, J = 15.7, 6.6 Hz, 1 H), 3.65 (d, J = 6.6 Hz, 2 H); 13C NMR
(CDCl3, 100 MHz) 140.3, 137.6, 131.2, 129.3, 128.8, 128.6, 127.2, 126.3, 126.2,
39.5.HRMS Cacld for C15H14: 194.1096; Found: 194.1094.
3b/3b′
3b/3b′ = 42:58. Colorless liquid. 1H NMR (CDCl3, 400 MHz) 7.55-7.24 (m, 9
H), 6.78 (d, J = 15.6 Hz, 0.4 H), 6.51-6.31 (m, 1.6 H), 3.69 (d, J = 6.9 Hz, 0.8 H), 3.64
13
(d, J = 4.8 Hz, 1.2 H), 2.46 (s, 1.3 H), 2.45 (s, 1.7 H); C NMR (CDCl3, 100 MHz)
140.4, 138.3, 137.6, 136.7, 136.5, 135.2, 131.0, 130.6, 130.3 x 2, 129.3, 129.1, 128.7,
128.6 x 2, 127.2, 126.5, 126.3, 126.2 x 3, 125.7, 39.8, 37.0, 20.0, 19.6. HRMS Cacld
for C16H16: 208.1252; Found: 208.1244.
3c/3c′
1
3c/3c′ Colorless liquid. The ratio of 3c/3c′ can not be determined by H NMR
spectroscopy. 1H NMR (CDCl3, 400 MHz) 7.47-7.28 (m, 7 H), 7.16-7.14 (m, 2 H),
6.57-6.41 (m, 2 H), 3.64-3.60 (m, 2 H), 2.43 (s, 2 H), 2.42 (s, 1 H); 13C NMR (CDCl3,
100 MHz) 140.4, 140.2, 138.2, 138.1, 137.6, 137.5, 131.2, 131.1, 129.6, 129.5, 129.1,
128.8, 128.6, 128.5, 128.0, 127.2, 127.0 x 2, 126.2, 125.8, 123.4, 39.5, 39.4, 21.5.
HRMS Cacld for C16H16: 208.1252; Found: 208.1253.
3d/3d′
3d/3d′ = 47:53. Colorless liquid. 1H NMR (CDCl3, 400 MHz) 7.45-7.18 (m, 9
H), 6.56-6.36 (m, 2 H), 3.63 (d, J = 6.8 Hz, 1.1 H), 3.60 (d, J = 6.7 Hz, 0.9 H), 2.43 (s,
13
1.4 H), 2.41 (s, 1.6 H); C NMR (CDCl3, 100 MHz) 140.5, 137.7, 137.2, 136.9,
135.8, 134.8, 131.0 x 2, 129.6, 129.3 x 2, 128.8, 128.7, 128.6 x 2, 128.3, 127.2, 126.2 x
7

2, 126.1, 39.5, 39.1, 21.3, 21.2. HRMS Cacld for C16H16: 208.1252; Found: 208.1260.
3d′′
1
3d′′ Colorless liquid. H NMR (CDCl3, 400 MHz) 7.33-7.29 (m, 2 H),
7.23-7.19 (m, 3 H), 7.14-7.09 (m, 4 H), 2.70-2.63 (m, 4 H), 2.35 (s, 3 H), 2.01-1.94 (m,
13
2 H); C NMR (CDCl3, 100 MHz) 142.5, 139.3, 135.3, 129.1, 128.6, 128.5, 128.4,
125.8, 35.6, 35.1, 33.2, 21.1. HRMS Cacld for C16H18: 210.1409; Found: 210.1405.
3e/3e′
1
3e/3e′ = 48:52. Colorless liquid. H NMR (CDCl3, 400 MHz) 7.43-7.22 (m, 7
H), 6.94-6.89 (m, 2 H), 6.52-6.25 (m, 2 H), 3.85 (s, 3 H), 3.59 (d, J = 6.8 Hz, 1 H),
13
3.56 (d, J = 6.4 Hz, 1 H); C NMR (CDCl3, 100 MHz) 159.0, 158.2, 140.6, 137.6,
132.3, 130.8, 130.5, 130.4, 129.8, 129.7, 128.8, 128.6 x 2, 127.3, 127.2, 126.2, 114.0,
55.4, 39.4, 38.6. HRMS Cacld for C16H16O: 224.1201; Found: 224.1205.
3f/3f′
1
3f/3f′ = 56:44. Colorless liquid. H NMR (CDCl3, 400 MHz) 7.46-7.26 (m, 7
H), 7.10-7.04 (m, 2 H), 6.55-6.32 (m, 2 H), 3.62 (d, J = 7.1 Hz, 0.9 H), 3.60 (d, J = 6.8
13
Hz, 1.1 H); C NMR (CDCl3, 100 MHz) 163.4, 162.8, 160.9, 160.4, 140.2, 137.4,
135.9, 135.8, 133.8, 133.7, 131.3, 130.2, 130.1, 130.0, 129.1 x 3, 128.8, 128.7, 127.7,
19
127.6, 127.3, 126.4, 126.3, 115.6, 115.4 x 2, 115.2, 39.4, 38.6; F NMR (CDCl3, 373
MHz)  -115.2 (d, J = 2.2 Hz), -117.1 (d, J = 2.5 Hz). HRMS Cacld for C15H13F:
212.1001; Found: 212.0991.
3f′′
1
3f′′ Colorless liquid. H NMR (CDCl3, 400 MHz) 7.34-7.28 (m, 2 H),
13
7.24-7.14 (m, 5 H), 7.01-6.97 (m, 2 H), 2.69-2.63 (m, 4 H), 2.01-1.93 (m, 2 H); C
NMR (CDCl3, 100 MHz) 162.4, 142.3, 138.0, 129.9, 129.8, 128.6, 128.5, 125.9,
115.3, 115.0, 35.5, 34.7, 33.2; 19F NMR (CDCl3, 373 MHz) -117.9. HRMS Cacld for
C15H15F: 214.1158; Found: 214.1160.
8

3g
1
3g White solid. H NMR (CDCl3, 400 MHz) 7.42-7.26m, 5 H, 6.53 (d, J =
13
15.7 Hz, 1 H), 6.27 (dt, J = 15.6, 6.8 Hz, 1 H), 3.64 (dd, J = 6.6, 1.0 Hz, 2 H); C
NMR (CDCl3, 100 MHz) 146.4, 143.9, 138.9, 136.7, 132.6, 128.7, 127.8, 126.4,
124.4, 113.4 x 2, 113.2 x 2, 25.8; 19F NMR (CDCl3, 373 MHz) -143.9 (dd, J = 22.4,
8.5 Hz), -157.3 (t, J = 20.8 Hz), 162.6 (td, J = 22.1, 8.4 Hz). HRMS Cacld for C15H9F5:
284.0624; Found: 284.0621.
3h/3h′
3h/3h′ = 66:34. Colorless liquid. 1H NMR (CDCl3, 400 MHz) 7.66-7.61 (m, 2
H), 7.51-7.28 (m, 7 H), 6.58-6.54 (m, 1.3 H), 6.44-6.37 (m, 0.6 H), 3.68-3.65 (m, 2 H);
13C NMR (CDCl3, 100 MHz) 144.4, 143.6, 141.1, 140.0, 137.3, 132.3, 132.1, 129.9,
129.1, 128.9, 128.8, 128.7 x 2, 128.6, 128.5, 128.0, 127.5, 126.5, 126.4, 126.3, 125.8,
125.7, 125.6 x 3, 125.5 x 2, 123.1 x 2, 39.5, 39.2; 19F NMR (CDCl3, 373 MHz) -62.2
(d, J = 40.0 Hz). HRMS Cacld for C16H13F3: 262.0969; Found: 262.0974.
3i/3i′
1
3i/3i′ = 69:31. White solid. H NMR (CDCl3, 400 MHz) 8.27-8.20 (m, 1 H),
8.01-7.95 (m, 1 H), 7.90-7.86 (m, 1 H), 7.72-7.28 (m, 9 H), 6.68-6.48 (m, 1.5 H), 4.11
13
(d, J = 4.7 Hz, 1.3 H), 3.80 (d, J = 6.8 Hz, 0.6 H); C NMR (CDCl3, 100 MHz)
140.3, 137.6, 136.3, 135.4, 134.0, 133.7, 132.5, 132.1, 131.4, 131.3, 129.0, 128.8,
128.7, 128.6 x 2, 128.5, 128.4, 127.6, 127.2, 126.5, 126.3, 126.2, 126.1, 126.0, 125.8 x
2, 125.7, 124.1, 124.0, 123.8, 39.8, 36.5. HRMS Cacld for C19H16: 244.1252; Found:
244.1258.
9

3j
3j Colorless liquid.1H NMR (CDCl3, 400 MHz) 7.43-7.35 (m, 6 H), 7.32-7.28
(m, 4 H), 6.50 (d, J = 15.8 Hz, 1 H), 6.34 (dt, J = 15.8, 6.7 Hz, 1 H), 2.88 (t, 2 H), 2.62
13
(q, 2 H); C NMR (CDCl3, 100 MHz) 141.9, 137.8, 130.6, 130.1, 128.6, 128.5,
127.1, 126.1, 126.0, 36.0, 35.0. HRMS Cacld for C16H16: 208.1259; Found: 208.1252.
4a/4a′
1
4a/4a′ Colorless liquid. H NMR (CDCl3, 400 MHz) 7.43-7.11 (m, 9 H),
13
6.53-6.39 (m, 2 H), 3.66-3.58 (m, 2 H), 2.41-2.40 (m, 2 H); C NMR (CDCl3, 100
MHz) 140.4, 140.3, 138.1, 137.7, 137.6, 136.9, 134.8, 131.3, 131.1, 129.6, 129.5,
129.3, 129.1, 128.8, 128.7, 128.6, 128.5, 128.3, 128.0, 127.2, 127.0, 126.3, 126.2,
123.4, 39.5, 39.1, 21.5, 21.3. HRMS Cacld for C16H16: 208.1252; Found: 208.1259.
4b/4b′
1
4b/4b′ Colorless liquid. H NMR (CDCl3, 400 MHz) 7.48-7.09 (m, 8 H),
6.85 (d, J = 15.4 Hz, 0.1 H), 6.57 (d, J = 16.4 Hz, 0.5 H), 6.51-6.38 (m, 1.2 H),
3.70-3.59 (m, 1 H), 2.42 -2.35 (m, 6 H); 13C NMR (CDCl3, 100 MHz) 140.5, 137.7 x
2, 136.7, 136.6, 135.6, 135.3, 134.4, 131.1, 130.1, 129.9 x 2, 129.7, 129.1, 128.8, 128.6
x 2, 128.1, 127.5, 127.4, 127.1, 126.2 x 2, 126.1, 123.7, 39.5, 39.1, 19.9, 19.6, 19.5.
HRMS Cacld for C17H18: 222.1409; Found: 222.1419.
4c/4c′
1
4c/4c′ Colorless liquid. H NMR (CDCl3, 400 MHz) 7.47-6.98 (m, 8 H), 6.76
(d, J = 15.6 Hz, 0.3 H), 6.59-6.40 (m, 1.3 H), 6.34-6.27 (m, 0.3 H), 3.69-3.59 (m, 2 H),
2.43 -2.41 (m, 6 H); 13C NMR (CDCl3, 100 MHz) 140.6, 138.1, 138.0, 137.7, 136.8,
136.3, 136.0, 135.2, 135.0, 133.9, 131.3, 131.2, 131.1, 130.9, 130.8, 129.7, 129.6,
129.3, 129.0, 128.8, 128.7, 128.6, 127.9, 127.1, 126.9, 126.8, 126.6, 126.2 x 3, 125.6,
124.2, 39.8, 39.5, 39.4, 36.6, 21.4, 21.2, 21.1, 19.9, 19.5. HRMS Cacld for C17H18:
10

222.1409; Found: 222.1413.
4d/4d′
4d/4d′ = 53:47. Colorless liquid. 1H NMR (CDCl3, 400 MHz) 7.46-7.28 (m, 6
H), 7.18-7.13 (m, 1.6 H), 7.09-7.05 (m, 1 H), 6.77 (d, J = 15.6 Hz, 0.4 H), 6.51-6.30
(m, 1.5 H), 3.68 (d, J = 7.0 Hz, 1 H), 3.60 (d, J = 5.3 Hz, 1 H), 2.42 (s, 3.3 H), 2.40 (s,
2.7 H); 13C NMR (CDCl3, 100 MHz) 140.5, 138.1, 137.7, 136.4, 135.6, 135.4, 133.3,
132.1, 130.9, 130.3, 130.2, 130.1, 129.2, 128.8 x 2, 128.6, 127.9, 127.2, 127.1, 126.3 x
2, 126.2, 39.8, 37.0, 21.1 x 2, 19.5, 19.1. HRMS Cacld for C19H16: 222.1409; Found:
222.1413.
4e/4e′
1
4e/4e′ = 58:42. Colorless liquid. H NMR (CDCl3, 400 MHz) 7.32-7.00 (m, 7
H), 6.91 (d, 0.4 H, J = 15.6 Hz), 6.44-6.23 (m, 1.5 H), 3.59 (d, 0.8 H, J = 6.9 Hz), 3.54
(d, 1.2 H, J = 6.0 Hz), 2.40-2.35 (m, 9 H); 13C NMR (CDCl3, 100 MHz) 138.3, 137.4,
136.8, 136.5, 135.7, 135.6, 135.4, 134.9, 133.3, 132.1, 130.8, 130.6, 130.2, 130.1,
129.3, 129.0, 128.6, 127.9, 127.7, 127.1, 126.4, 126.1, 39.4, 37.0, 21.3, 21.1 x 3, 19.5,
19.1. HRMS Cacld for C18H20: 236.1565; Found: 236.1566.
4f
4f Colorless liquid. 1H NMR (CDCl3, 400 MHz) 7.24 (s, 1 H), 7.08 (d, J = 7.6
Hz, 1 H), 7.02 (d, J = 7.6 Hz, 1 H), 6.77 (d, J = 15.5 Hz, 1 H), 6.12 (dt, J = 15.2, 6.8
13
Hz, 1 H), 3.67 (d, J = 6.8 Hz, 2 H), 2.35 (d, J = 5.7 Hz, 6 H); C NMR (CDCl3, 100
MHz) 146.4, 144.0, 141.2, 138.8, 136.4, 135.6 x 2, 132.4, 130.8, 130.3, 128.5, 126.3,
19
125.4, 113.7, 113.6, 113.5, 29.9, 21.0, 19.3; F NMR (CDCl3, 373 MHz) -144.0 to
-144.1 (m, 2 F), -157.4 to -157.5 (m, 1 F), -162.6 to -162.7 (m, 2 F). HRMS Cacld for
11

C17H13F5: 312.0937; Found: 312.0933.
4g/4g′
1
4g/4g′ Colorless liquid. H NMR (CDCl3, 400 MHz) 7.45-7.14 (m, 9 H),
13
6.55-6.28 (m, 2 H), 3.67-3.59 (m, 2 H), 2.79-2.67 (m, 2 H), 1.34-1.29 (m, 3 H); C
NMR (CDCl3, 100 MHz) 144.6 x 2, 143.4, 142.2, 140.5, 140.3, 137.7, 137.6, 137.5,
135.1, 131.4, 131.1, 131.0, 129.6, 129.5, 129.1, 128.8 x 2, 128.7, 128.6, 128.4, 128.1 x
2, 127.2, 126.9, 126.2, 126.1, 125.8, 123.7, 39.5 x 2, 39.1, 29.0. 28.7, 28.6, 15.8 x 2,
15.7. HRMS Cacld for C17H18: 222.1409; Found: 222.1415.
4h/4h′
1
4h/4h′ Colorless liquid. H NMR (CDCl3, 400 MHz) 7.45-7.12 (m, 9 H),
6.57-6.29 (m, 2 H), 3.67-3.60 (m, 2 H), 2.75-2.63 (m, 2 H), 1.75-1.69 (m, 2 H),
13
1.10-1.01 (m, 3 H); C NMR (CDCl3, 100 MHz) 143.1, 143.0, 141.8, 140.7, 140.5,
140.4, 140.1, 137.7, 137.5, 135.1, 131.4, 131.1 x 2, 130.9, 129.6, 129.5, 129.1, 129.0,
128.8 x 3, 128.7, 128.6, 128.5, 128.3, 127.5, 127.2, 126.4, 126.2, 126.1, 123.7, 39.5 x 2,
39.1, 38.2 x 2, 37.9, 37.8, 24.8, 24.7 x 2, 14.1, 14.0, 13.9. HRMS Cacld for C18H20:
236.1565; Found: 236.1570.
4i/4i′
1
4i/4i′ = 58:42. Colorless liquid. H NMR (CDCl3, 400 MHz) 7.43-7.21 (m, 7
H), 7.03-6.82 (m, 2 H), 6.52-6.37 (m, 1.4 H), 6.32-6.25 (m, 0.4 H), 3.85 (s, 3 H), 3.59
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(d, J = 7.0 Hz, 1.1 H), 3.55 (d, J = 6.4 Hz, 0.8 H); C NMR (CDCl3, 100 MHz)
158.9, 158.1, 140.5, 137.6, 130.5, 129.7 x 2, 128.7, 128.5 x 2, 127.3, 127.1, 126.2,
114.0, 55.3, 39.4, 38.5. HRMS Cacld for C16H16O: 224.1201; Found: 224.1209.
4j/4j′
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4j/4j′ Colorless liquid. H NMR (CDCl3, 400 MHz) 7.45-7.19 (m, 7 H),
7.16-6.94 (m, 2 H), 6.80 (d, J = 16.0 Hz, 0.2 H), 6.52-6.29 (m, 1.7 H), 3.62-3.55 (m, 2
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H); C NMR (CDCl3, 100 MHz) 162.4, 161.9, 137.5, 131.6, 128.8, 128.7, 128.6,
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128.4, 127.7, 127.3, 126.3, 115.5 x 2, 39.9, 39.4, 38.6, 32.4, 32.3; F NMR (CDCl3,
373 MHz)  -113.5, -113.7, -115.3, -117.2, -118.4, -118.6. HRMS Cacld for C15H13F:
212.1001; Found: 212.1006.
4k/4k′
4k/4k′ Colorless liquid. 1H NMR (CDCl3, 400 MHz) 7.49-7.16 (m, 9 H), 6.92
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(d, J = 15.7 Hz, 0.1 H), 6.53-6.34 (m, 1.8 H), 3.79-3.55 (m, 2 H); C NMR (CDCl3,
100 MHz) 140.0, 139.8, 139.5, 138.0, 137.5, 137.3, 131.8, 130.1, 129.8, 129.6, 128.9,
128.8 x 2, 128.7, 128.6, 128.3, 127.4 x 2, 127.3, 127.2, 127.0 x 2, 126.5, 126.4 x 2,
126.3 x 2, 126.2, 124.5, 39.4 x 2, 39.1, 38.7, 36.9. HRMS Cacld for C15H13Cl:
228.0706; Found: 228.0702.
3a-d5
1
3a-d5 Colorless liquid. H NMR (CDCl3, 400 MHz) 7.36-7.12m, 6 H, 6.46
(d, J = 15.7 Hz, 1 H), 6.39-6.32 (m, 1 H), 3.55 (d, J = 6.6 Hz, 2 H); 13C NMR (CDCl3,
100 MHz) 140.3, 137.6, 131.2 x 2, 129.4, 129.3, 128.8, 128.6, 127.2, 126.3 x 2, 39.5,
39.4.HRMS Cacld for C15H9D5: 194.1409; Found: 194.1410.
4l-d7
1
4l-d7 Colorless liquid. H NMR (CDCl3, 400 MHz) 8.20-8.11 (m, 1.5 H),
7.94-7.89 (m, 3 H), 7.67-7.45 (m, 6 H), 7.28-7.16 (m, 1 H), 6.76 (d, J = 15.7 Hz, 0.2
H), 6.58-6.40 (m, 2 H), 4.10-4.05 (m, 2 H), 3.72-3.69 (m, 1 H); 13C NMR (CDCl3, 100
MHz) 138.1, 137.5, 136.9, 136.8, 136.5, 136.4, 135.2, 134.8, 134.0, 132.2, 131.5,
131.3, 130.4, 130.3, 129.6, 129.5, 129.3 x 2, 128.8, 128.7 x 2, 128.6, 128.5, 128.0,
127.9, 127.8, 127.6, 127.2, 127.1 x 2, 127.0, 126.6, 126.5 x 2, 126.4, 126.3, 126.1,
126.0 x 3, 125.8 x 2, 125.7, 124.2, 124.0, 123.8, 123.4, 36.9, 36.5, 21.5, 21.3, 19.9.
HRMS Cacld for C20H11D7: 265.1848; Found: 265.1850.
6. The crystal structure of (E)-3i
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X-Ray crystallographic study: Single crystal X-ray diffraction study for
compound (E)-3i was carried out on a Bruker CCD area detector diffractometer with
graphite-monochromated Mo Kα radiation (λ= 0.71073 Å). Cell parameters were
obtained by global refinement of the positions of all collected reflections. Intensities
were corrected for Lorentz and polarization effects and empirical absorption. The
structure was solved by direct methods and refined by full-matrix least squares on F2.
All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were placed
in calculated positions. Structure solution and refinement were performed by using the
SHELXL-97 package. The X-ray crystallographic files, in CIF format, are available
from the Cambridge Crystallographic Data Centre on quoting the deposition numbers
CCDC 969149 for (E)-3i. Copies of this information may be obtained free of charge
from The Director, CCDC, 12 Union Road, Cambridge CB2 IEZ, UK (Fax:
+44-1223-336033;
ccdc.cam.ac.uk).
e-mail:
deposit@ccdc.cam.ac.ukor
www:
http://www.
Figure 1. Molecular structure of (E)-3i.
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7. Copies of NMR and HRMS spectra
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