Biaryl construction through kumada coupling with diaryl sulfates as one-by-one electrophiles under mild conditions

Article abstract of DOI:10.1021/ol9028308

(Figure presented) Diaryl sulfates were successfully applied as one-by-one organo electrophiles in Kumada coupling to construct biaryls with the emission of harmless Inorganic salts.

Full text of DOI:10.1021/ol9028308

Supporting information for
Biaryl Construction through Kumada Coupling with Diaryl
Sulfates as One-by-one Electrophiles under Mild Condition
Bing-Tao Guan, Xing-Yu Lu, Yang Zheng, Da-Gang Yu, Tong Wu, Kun-Lin Li,
Zhang-Jie Shi*
*Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory
of Bioorganic Chemistry and Molecular Engineering of Ministry of Education,
College of Chemistry and Green Chemistry Center, Peking University, Beijing
100871, China
Phone: +86 (10) 6276-0890, zshi@pku.edu.cn
Table
Page
2
General
2-5
6-12
13
Synthesis and analytical data of diaryl sulfates 1
Synthesis and analytical data of biaryl products 3
Mechanism exploration
1H and 13C NMR spectral data
Reference
14-45
46
1

General: All reactions were carried out under N2 atmosphere. All the reagents were
purchased from Alfa Aesar and Acros Chemical and used without further purification.
The Grignard reagents were newly prepared in THF while phenylmagnesium bromide
was purchased from Aldrich and used without further purification. The concerntration
of the Grignard reagents was determined by the Acid-Base Titration. NiCl2(PCy3)2
was synthesized according to literature method.1 The solvent was freshly distilled
over sodium with the use of diphenyl ketone as an indicator. 1H NMR (300 MHz) and
13C NMR (75 MHz) were registered on 300M spectrometers with CDCl3 as solvent
and tetramethylsilane (TMS) as internal standard. Chemical shifts were reported in
units (ppm) by assigning TMS resonance in the 1H spectrum as 0.00 ppm and CDCl3
13
resonance in the C spectrum as 77.0 ppm. All coupling constants (J values) were
reported in Hertz (Hz). Column chromatography was performed on silica gel 200-300
mesh. GC, HPLC and MS were performed by the Analytical Center in Peking
University.
Condition for the Suzuki reaction from compound 18 to compound 19
0.2 mmol (80.2 mg) 18, 0.3 mmol (72.6 mg) phenylboronic acid, 0.02 mmol (10mg)
Pd(OAc)2, 0.4 mmol (84.8 mg) Na2CO3 were added in a sealed tube under N2. 1.4mL
H2O and 1.2 mL acetone were injected in to the mixture. The reaction was stirred for
1 h under room temperature. The reaction was washed by 25mL H2O and extracted by
25×3mL CH2Cl2. The solvent was removed and the pure product was separated
through a flash column chromatography (CH2Cl2 : PE=1:5) as a white solid. The yield
was 84%.
Method A: General procedure for the syntheses of diaryl sulfates:
The phenol(15 mmol), 1.63g Cs2CO3(5mmol), 0.99g N,N'-sulfuryldiimidazole (5
mmol) and 5mL THF were added in a 20mL of dry tube. Then the mixture was heated
to reflux and stirred overnight. The mixture was cooled to room temperature and then
filtered through a short silicon column. After concentration of the filtrate, the diaryl
sulfates was purified by column chromatography. The yields reported here were based
on N,N'-sulfuryldiimidazole and the addition of excess phenol could restrain the
generation of monosulfates. The excessive phenol could easily be removed from the
system and recycled in large scale.
By a simple scale-up, 100 gram of di(p-tolyl) sulfate 1a was produced without the
change of the procedure in an excellent yield.
2

Di(p-tolyl) sulfate (1a). The product was made following method A with a yield of
95% as a white solid. 1H NMR (300 MHz, CDCl3): δ 7.20 (s, 8 H), 2.36 (s, 6 H). 13C
NMR (75.4 MHz, CDCl3): δ 148.5, 137.6, 130.5, 120.8, 20.8. ESI-MS m/z: 301.0503
[M+Na]+, calcd. for C14H14NaO4S: 301.0510. IR (KBr, cm-1): ν 2924, 1501, 1459,
1378, 1216, 1179, 1145, 881.
dinaphthalen-2-yl sulfate (1b) The product was made following method A with a
1
yield of 94% as a white solid. H NMR (300 MHz, CDCl3): δ 7.84-7.93 (m, 8H),
7.54-7.57 (m, 4H). 7.43-7.47 (m, 2H). C NMR (75.4 MHz, CDCl3): 148.0, 133.5,
13
132.1, 130.4, 128.0, 127.9, 127.3, 126.8, 119.7, 118.7. ESI-MS m/z: 373.0498
[M+Na]+, calcd. for C20H14NaO4S: 373.0510. IR (KBr, cm-1): ν 2925, 1511, 1461,
1415, 1196, 1110, 912.
Di(m-tolyl) sulfate (1c) The product was made following method A with a yield of
1
94% as a colorless oil. H NMR (300 MHz, CDCl3): δ 7.26-7.33 (m, 2 H), 7.11-7.16
(m, 6 H), 2.38 (s, 6 H). C NMR (75.4 MHz, CDCl3): 150.5, 140.6, 129.7, 128.4,
13
121.6, 118.0, 21.2. ESI-MS m/z: 301.5052 [M+Na]+, calcd. for C14H14NaO4S:
301.0510.
IR (KBr, cm-1): ν 2923, 1585, 1488, 1460, 1417, 1201, 1125, 929, 848.
Di(o-tolyl) sulfate (1d) The product was made following method A with a yield of
95% as a yellow oil. 1H NMR (300 MHz, CDCl3): δ 7.21-7.34 (m, 8 H), 2.32 (s, 6 H).
13C NMR (75.4 MHz, CDCl3): δ 149.2, 132.0, 131.1, 127.7, 127.4, 121.2, 16.1 MS
(EI) m/z: 204 (M+). ESI-MS m/z: 301.0501 [M+Na]+, calcd. for C14H14NaO4S:
301.0510.
IR (KBr, cm-1): ν 2925, 1491, 1398, 1207, 1152, 1097, 882.
3

diphenyl sulfate (1e) The product was made following method A with a yield of 90%
1
as a yellow oil. H NMR (300 MHz, CDCl3): 7.39-7.45 (m, 4H), 7.30-7.36 (m, 6H).
13C NMR (75.4 MHz, CDCl3): δ 150.5, 130.1, 127.7, 121.1. ESI-MS m/z: 273.0192
[M+Na]+, calcd. for C12H10NaO4S: 273.0197. IR (KBr, cm-1): ν 1487, 1415, 1400,
1215, 1143, 876.
bis(4-methoxyphenyl) sulfate (1f) The product was made following method A with a
1
yield of 89% as a white solid. H NMR (300 MHz, CDCl3): δ 7.24 (d, J = 9.0 Hz ,4
13
H), 6.91 (d, J = 9.0 Hz , 4 H). 3.82 (s, 6 H). C NMR (75.4 MHz, CDCl3): δ 158.7,
144.0, 122.3, 114.9, 55.6. ESI-MS m/z: 333.0403 [M+Na]+, calcd. for C14H14NaO6S:
333.0409. IR (KBr, cm-1): ν 2924, 1500, 1253, 1169, 1032, 884.
bis(2-methoxyphenyl) sulfate (1g) The product was made following method A with a
1
yield of 95% as a white solid. H NMR (300 MHz, CDCl3): δ 7.44- (m, 2H),
13
7.11-7.16 (m, 2H), 7.11-7.16 (m, 4H), 3.87 (s, 6H). C NMR (75.4 MHz, CDCl3): δ
151.7, 139.7, 128.4, 122.8, 120.7, 113.2, 56.0. ESI-MS m/z: 333.0400 [M+Na]+, calcd.
for C14H14NaO6S : 333.0409. IR (KBr, cm-1): ν 2924, 1501, 1414, 1283, 1261, 1214,
1154, 1104, 888.
bis(4-(dimethylamino)phenyl) sulfate (1h) The product was made following method
A with a yield of 95% as a white solid. 1H NMR (300 MHz, CDCl3): 7.17 (d, J = 9.6
13
Hz, 4H), 6.66 (d, J = 9.3 Hz, 4H) 2.95 (s, 12H). C NMR (75.4 MHz, CDCl3): δ
149.7, 141.3, 121.8, 112.7, 40.6. ESI-MS m/z:337.1212 [M+Na]+, calcd. for
C16H21N2O4S: 337.1222. IR (KBr, cm-1): ν 2921, 1603, 1513, 1446, 1396, 1369, 1235,
1177, 1142, 1068, 948, 873, 813.
4

bis(4-(2-(2-methyl-1,3-dioxolan-2-yl)ethyl)phenyl) sulfate (15) In a 20mL dry tube,
1.64g 4-(4-hydroxyphenyl)butan-2-one (10 mmol), 1.63g Cs2CO3(5mmol) and 990mg
N,N'-sulfuryldiimidazole (5 mmol) were added. Then 5mL THF was injected in the
mixture. The reaction was refluxed overnight. The mixture was cooled to room
temperature and then filtered through a short silicon column. The solvent was
removed and the product (bis(4-(3-oxobutyl)phenyl) sulfate) was purified by column
chromatography as a white solid with a yield of 83%. 0.72g bis(4-(3-oxobutyl)phenyl)
sulfate (2mmol), 0.37g ethane-1,2-diol (6mmol), 0.084g TsOH·H2O(0.2mmol) and
10mL toluene were added into a 50mL flask. The mixture was refluxed overnight
with a Dean-Stark trap. The reaction was cooled to room temperature and washed by
brine (25mL×3). The organic layer was dried by the MgSO4. The solvent was
removed and the product (bis(4-(2-(2-methyl-1,3-dioxolan-2-yl)ethyl)phenyl) sulfate)
1
was purified by column chromatography as a white solid with a yield of 97.5%. H
NMR (300 MHz, CDCl3): δ 7.24-7.27 (m, 8H), 3.96-4.02 (m, 8H) , 2.71-2.77 (m,
13
4H) , 1.93-1.99 (m, 4H), 1.37 (s, 6H). C NMR (75.4 MHz, CDCl3): 129.8, 121.0,
109.5, 64.8, 40.8, 29.5, 23.9. ESI-MS m/z: 501.1545 [M+Na]+, calcd. for
C24H30NaO8S: 501.1559. IR (KBr, cm-1): ν 2927, 1500, 1413, 1375, 1256, 1212, 1147,
1056, 883.
bis(4-bromophenyl) sulfate (17) The product was made following method A with a
yield of 93% as a white solid. 1H NMR (300 MHz, CDCl3): 7.55 (d, J = 9.0 Hz, 1H),
7.19 (d, J = 8.7 Hz, 2H). 13C NMR (75.4 MHz, CDCl3): δ 149.2, 133.3, 122.8, 121.3.
ESI-MS m/z: 428.8393 [M+Na]+, calcd. for C12H8Br2NaO4S: 428.8408. IR (KBr,
cm-1): ν 1477, 1418, 1218, 1147, 1067, 1012, 878, 831, 775.
Di(biphenyl-4-yl) sulfate (18) The product was made following method A with a
yield of 65% as a white solid. 1H NMR (300 MHz, CDCl3): δ 7.63 (d, J = 9.0 Hz, 4H),
7.56 (d, J = 7.2 Hz, 4H), 7.35-7.48 (m, 10H). 13C NMR (75.4 MHz, CDCl3): δ 149.8,
141.1, 139.7, 129.0, 128.8, 127.9, 127.2, 121.4. ESI-MS m/z: 425.0808 [M+Na]+,
5

calcd. for C24H18NaO4S: 425.0823. IR (KBr, cm-1): ν 3033, 1510, 1483, 1420, 1400,
1218, 1151, 879, 762.
Method B: General procedure for syntheses of biaryl product 3
NiCl2(PCy3)2 (6.8, 0.01 mmol), PCy3 (5.6 mg, 0.02 mmol), diarylsulfates (0.2 mmol),
newly made Grignard reagent (0.6mL 1M, 0.6mmol) and 2 mL freshly distilled
diethylether were added into a dry Schlenck tube under a nitrogen atmosphere at room
temperature. The reaction mixture was stirred for 2 h under room temperature. After
that, about 0.5g silica gel was added to quench the reaction. Then the mixture was
filtered through a short silicon column. After concentration of the filtrate, the biaryl
product 3 was purified by column chromatography.
2-phenylnaphthalene.[1](3ba) The product was made following method B with a
yield of 85% as a white solid. 1H NMR (300 MHz, CDCl3): δ 8.00 (s, 1H), 7.79-7.86
(m, 3H), 7.66-7.71 (m, 3H), 7.40-7.45 (m, 4H), 7.30-7.35 (m, 1H). C NMR (75.4
13
MHz, CDCl3): δ 141.2, 138.6, 133.7, 132.7, 128.9, 128.5, 128.2, 127.7, 127.5, 127.4,
126.3, 125.9, 125.8, 125.6. MS (EI) m/z: 204 (M+). IR (KBr, cm-1): ν 3056, 1597,
1495, 1453, 1265, 894, 859, 821, 738.
2-(o-tolyl)naphthalene.[1] (3bb) The product was made following method B with a
1
yield of 93% as a colorless oil. H NMR (300 MHz, CDCl3): δ 7.79-7.83 (m, 3H),
7.74 (s, 1H), 7.42-7.46 (m, 3H), 7.24-7.31 (m, 4H), 2.28 (s, 3H). C NMR (75.4
13
MHz, CDCl3): δ 141.9, 139.6, 135.6, 133.4, 132.3, 130.4, 130.1, 128.0, 127.83,
127.77, 127.72, 127.5, 127.4, 126.2, 125.9, 20.4. MS (EI) m/z: 218 (M+). IR (KBr,
cm-1): ν 3054, 1598, 1491, 1458, 1130, 1026, 857, 821, 757.
2-(m-tolyl)naphthalene.[2] (3bc) The product was made following method B with a
1
yield of 94% as a colorless oil. H NMR (300 MHz, CDCl3): δ 8.02 (s, 1H),
6

7.83-7.91(m, 3H), 7.73 (dd, J = 1.8, 8.6 Hz, 1H), 7.45-7.53 (m, 4H), 7.36 (t, J = 7.5
Hz, 1H), 7.19 (d, J = 7.2 Hz, 1H), 2.44 (s, 3H). 13C NMR (75.4 MHz, CDCl3): δ 141.2,
138.7, 138.5, 133.7, 132.7, 128.8, 128.4, 128.3, 128.24, 128.16, 127.7, 126.3, 125.9,
125.8, 125.7, 124.6, 21.5. MS (EI) m/z: 218 (M+). IR (KBr, cm-1): ν 3054, 1605, 1490,
856, 784, 745, 701.
2-(p-tolyl)naphthalene.[3] (3bd) The product was made following method B with a
yield of 93% as a white solid (An 87% yield was obtained in a 10 mmol scale in the
presence of 1 mol% catalyst). 1H NMR (300 MHz, CDCl3): δ 7.98 (d, J = 1.8 Hz, 1H),
7.78-7.85 (m, 3H), 7.69 (dd, J = 1.5, 8.4 Hz, 1H), 7.58 (d, J = 8.4 Hz, 2H), 7.41-7.47
(m, 2H), 7.24 (d, J = 7.8 Hz, 2H), 2.37 (s, 3H). 13C NMR (75.4 MHz, CDCl3): δ 138.5,
138.2, 137.2, 133.8, 132.5, 129.6, 128.4, 128.2, 127.7, 127.3, 126.2, 125.8, 125.6,
125.4, 21.0. MS (EI) m/z: 218 (M+). IR (KBr, cm-1): ν 3058, 1502, 1265, 1131, 1019,
907, 810, 731.
2-(4-methoxyphenyl)naphthalene.[1] (3be) The product was made following method
1
B with a yield of 88% as a white solid. H NMR (300 MHz, CDCl3): δ 7.97 (s, 1H),
7.80-7.87 (m, 3H), 7.69 (dd, J = 1.8, 8.6 Hz, 1H), 7.63 (d, J = 8.4 Hz, 2H), 7.41-7.49
(m, 2H), 6.99 (d, J = 8.7 Hz, 2H), 3.82 (s, 3H). 13C NMR (75.4 MHz, CDCl3): δ 159.3,
138.2, 133.8, 133.6, 132.4, 128.45, 128.39, 128.1, 127.7, 126.3, 125.7, 125.4, 125.0,
114.3, 55.3. MS (EI) m/z: 234 (M+). IR (KBr, cm-1): ν 2956, 1607, 1521, 1503, 1283,
1253, 1184, 1039, 814, 742
N,N-dimethyl-4-(naphthalen-2-yl)aniline.[1] (3bf) The product was made following
method B with a yield of 92% as a white solid. 1H NMR (300 MHz, CDCl3): δ 8.07 (s,
1H), 7.89-7.95 (m, 3H), 7.79-7.83 (m, 1H), 7.72 (d, J = 8.7 Hz, 2H), 7.47-7.57 (m,
13
2H), 6.91 (d, J = 9.0 Hz, 2H), 3.06 (s, 6H). C NMR (75.4 MHz, CDCl3): δ 150.1,
7

138.6, 133.9, 132.1, 129.0, 128.2, 128.0, 127.6, 126.1, 125.32, 125.26, 124.2, 112.9,
40.4. MS (EI) m/z: 247 (M+). IR (KBr, cm-1): ν 2850, 1607, 1528, 1503, 1354, 1231,
1065, 945, 857, 810, 742.
2-mesitylnaphthalene.[4] (3bg) The product was made following method B with a
1
yield of 91% as a colorless oil. H NMR (300 MHz, CDCl3): δ 7.80-7.90 (m, 3H),
7.60 (s, 1H), 7.47-7.50 (m, 2H), 7.28 (dd, J = 1.6, 8.3 Hz, 1H), 6.97 (s, 2H), 2.35 (s,
3H), 2.02 (s, 6H). 13C NMR (75.4 MHz, CDCl3): δ 138.9, 138.7, 136.8, 136.2, 133.6,
132.3, 128.2, 128.02, 127.96, 127.92, 127.8, 126.0, 125.7, 21.0, 20.7. MS (EI) m/z:
246 (M+). IR (KBr, cm-1): ν 2981, 1488, 1377, 1128, 1025, 895, 852, 820.
2-(4-fluorophenyl)naphthalene.[1] (3bh) The product was made following method B
1
with a yield of 72% as a white solid. H NMR (300 MHz, CDCl3): δ 7.92 (s, 1 H),
7.80-7.86 (m, 3 H), 7.58-7.64 (m, 3 H), 7.41-7.49 (m, 2 H), 7.09-7.14 (m, 2H). C
13
NMR (75.4 MHz, CDCl3): δ 162.6 (d, JC-F = 244.6 Hz), 137.6, 137.3 (d, JC-F = 3.2 Hz),
133.7, 132.6, 129.0 (d, JC-F = 8.2 Hz), 128.6, 128.2, 127.7, 126.4, 126.0, 125.7, 125.4,
115.7 (d, JC-F = 20.6 Hz). MS (EI) m/z: 222 (M+). IR (KBr, cm-1): ν 3059, 1602, 1512,
1500, 1221, 1157, 1094, 822, 747.
2-(4-chlorophenyl)naphthalene.[5] (3bi) The product was made following method B
with a yield of 43% as a white solid. 1H NMR (300 MHz, CDCl3): δ 7.96 (s, 1H), 7.
82-7.88 (m, 3H), 7.64 (dd, J = 1.8, 8.4 Hz, 1H), 7.59 (d, J = 8.4 Hz, 2H), 7.46-7.51 (m,
2H), 7.41 (d, J = 8.4 Hz, 2H). 13C NMR (75.4 MHz, CDCl3): δ 139.6, 137.3, 133.7,
133.5, 132.7, 129.0, 128.7, 128.2, 127.7, 126.5, 126.2, 125.8, 125.2. MS (EI) m/z: 238
(M+). IR (KBr, cm-1): ν 2923, 1494, 1400, 1094, 1011, 816, 750.
8

4-methoxybiphenyl.[2] (3fa) The product was made following method B with a yield
of 72% as a white solid. 1H NMR (300 MHz, CDCl3): δ 7.52-7.57 (m, 4H), 7. 39-7.44
(m, 2H), 7.23-7.33 (m, 1H), 6.98 (d, J = 9.0 Hz, 2H), 3.84 (s, 3H). C NMR (75.4
13
MHz, CDCl3): δ 159.0, 140.7, 133.7, 128.7, 128.1, 126.7, 126.6, 114.1, 55.2. MS (EI)
m/z: 184 (M+). IR (KBr, cm-1): ν 3003, 2961, 2837, 1608, 1519, 1487, 1246, 1183,
1043, 907, 834, 732.
4-methoxy-4'-methylbiphenyl.[6](3fb) The product was made following method B
1
with a yield of 75% as a white solid. H NMR (300 MHz, CDCl3): δ 7.50 (d, J = 8.7
Hz, 2H), 7. 44 (d, J = 7.8 Hz, 2H), 7.21 (d, J = 7.8 Hz, 2H), 6.95 (d, J = 9.0 Hz, 2H),
3.81 (s, 3H), 2.36 (s, 3H). 13C NMR (75.4 MHz, CDCl3): δ 158.9, 137.9, 136.3, 133.7,
129.4, 127.9, 126.5, 114.1, 55.2, 21.0. MS (EI) m/z: 198 (M+). IR (KBr, cm-1): ν 2913,
1607, 1500, 1288, 1249, 1182, 1038, 907, 808, 732.
4'-methoxy-3-methylbiphenyl.[7] (3fc) The product was made following method B
1
with a yield of 73% as a white solid. H NMR (300 MHz, CDCl3): δ 7.52 (d, J = 8.4
Hz, 2H), 7. 24-7.37 (m, 3H), 7.12 (d, J = 6.9 Hz, 1H), 6.96 (d, J = 8.4 Hz, 2H), 3.84 (s,
3H), 2.41 (s, 3H). 13C NMR (75.4 MHz, CDCl3): δ 159.2, 140.9, 138.4, 134.0, 128.7,
128.2, 127.6, 127.5, 123.9, 114.2, 55.3, 21.4. MS (EI) m/z: 198(M+). IR (KBr, cm-1): ν
2911, 1603, 1515, 1484, 1248, 1186, 1030, 837, 785.
4'-methoxy-2-methylbiphenyl.[7] (3fd) The product was made following method B
1
with a yield of 75% as a colorless oil. H NMR (300 MHz, CDCl3): δ 7.21-7.26 (m,
6H), 6.95 (d, J = 9 Hz, 2H), 3.84 (s, 3H), 2.27 (s, 3H). 13C NMR (75.4 MHz,
CDCl3): δ 158.6, 141.6, 135.5, 134.4, 130.4, 130.3, 130.0, 127.0, 125.8, 113.5, 55.2,
20.4. MS (EI) m/z: 198 (M+). IR (KBr, cm-1): ν 2954, 2931, 2835, 1621, 1516, 1483,
1464, 1243, 1176, 1038, 833, 760, 731.
9

2-methoxy-4'-methylbiphenyl.[8] (3gb) The product was made following method B
1
with a yield of 75% as a white solid. H NMR (300 MHz, CDCl3): δ 7.43 (d, J = 7.8
Hz, 2H), 7.20-7.32 (m, 4H), 6.94-7.03 (m, 2H), 3.77 (s, 3H), 2.37 (s, 3H). C NMR
13
(75.4 MHz, CDCl3): δ 156.5, 136.5, 135.6, 130.73, 130.65, 129.4, 128.7, 128.3, 120.7,
111.1, 55.4, 21.2. MS (EI) m/z: 198 (M+). IR (KBr, cm-1) : ν 2920, 1597, 1486, 1260,
1235, 1180, 1123, 1029, 819, 753.
N,N-dimethylbiphenyl-4-amine.[9] (3ha) The product was made following method B
with a yield of 83% as a yellow oil. 1H NMR (300 MHz, CDCl3): δ 7.49-7.57 (m, 4H),
7.36-7.41 (m, 2H), 7.23-7.27 (m, 1H), 6.81 (d, J = 9 Hz, 3H), 3.06 (s, 3H). 13C NMR
(75.4 MHz, CDCl3): δ 150.0, 141.3, 129.4, 128.7, 127.8, 126.4, 126.0, 112.9, 40.5.
ESI-MS m/z: 198.1 [M+H]+. IR (KBr, cm-1) : ν 2917, 1719, 1610, 1507, 1369, 1286,
911, 812.
N,N,4'-trimethylbiphenyl-4-amine.[10] (3hb) The product was made following
1
method B with a yield of 81% as a white solid. H NMR (300 MHz, CDCl3): δ
7.43-7.49 (m, 4H), 7.19 (d, J = 8.1 Hz, 2H), 6.78 (d, J = 8.4 Hz, 2H), 2.95 (s, 6H),
13
2.36 (s, 3H). C NMR (75.4 MHz, CDCl3): δ 149.9, 138.4, 135.6, 129.41, 129.35,
127.5, 126.2, 112.8, 40.5, 20.9. ESI-MS m/z: 212.1 [M+H]+. IR (KBr, cm-1) : ν 2916,
1681, 1607, 1503, 1351, 1220, 1160, 1114, 946, 807, 731.
N,N,3'-trimethylbiphenyl-4-amine. (3hc) The product was made following method
B with a yield of 88% as a yellow oil. 1H NMR (300 MHz, CDCl3): δ 7.50 (d, J = 9.0
Hz, 2H), 7.28-7.37 (m, 3H), 7.08 (d, J = 7.8 Hz, 1H), 6.81 (d, J = 9.0 Hz, 2H), 2.97 (s,
6H), 2.39 (s, 3H). 13C NMR (75.4 MHz, CDCl3): δ 150.0, 141.3, 138.2, 129.5, 128.6,
127.8, 127.2, 126.8, 123.5, 112.8, 40.5, 21.5. ESI-MS m/z: 212.1 [M+H]+. IR (KBr,
cm-1) : ν 2918, 1678, 1605, 1525, 1485, 1444, 1352, 1225, 1200, 1166, 946, 819, 781.
10

N,N-dimethyl-4-(naphthalen-2-yl)aniline.[1] (3hj) The product was made following
method B with a yield of 73% as a white solid. 1H NMR (300 MHz, CDCl3): δ 8.13 (s,
1H), 7.95-8.00 (m, 3H), 7.85-7.89 (m, 1H), 7.78 (d, J = 8.7 Hz, 2H), 7.53-7.63 (m,
13
2H), 6.95 (d, J = 9.0 Hz, 2H), 3.01 (s, 6H). C NMR (75.4 MHz, CDCl3): δ 150.0,
138.6, 133.9, 132.1, 128.9, 128.2, 128.0, 127.6, 126.1, 125.29, 125.24, 124.1, 112.8,
40.3. MS (EI) m/z: 247 (M+). IR (KBr, cm-1): ν 2850, 1607, 1528, 1503, 1354, 1231,
1065, 945, 857, 810, 742.
N,N-dimethyl-4-(naphthalen-1-yl)aniline.[11] (3hk) The product was made
1
following method B with a yield of 61% as a colorless oil. H NMR (300 MHz,
CDCl3): δ 8.02 (d, J = 7.5 Hz, 1H), 7. 85 (d, J = 8.1 Hz, 1H), 7.77 (d, J = 8.1 Hz, 1H),
7.37-7.49 (m, 6H), 6.82 (d, J = 8.7 Hz, 2H), 2.97 (s, 3H). C NMR (75.4 MHz,
13
CDCl3): δ 149.8, 140.5, 134.0, 132.0, 130.8, 128.8, 128.2, 126.9, 126.8, 126.4, 125.7,
125.6, 125.5, 112.3, 40.5. MS (EI) m/z: 247 (M+). IR (KBr, cm-1): ν 3040, 2848, 1395,
1352, 1197, 800, 776.
2-methyl-2-(2-(4'-methylbiphenyl-4-yl)ethyl)-1,3-dioxolane. (16) The product was
1
made following method B with a yield of 66% as a white solid. H NMR (300 MHz,
CDCl3): δ 7.47-7.52 (m, 4H), 7.22-7.28 (m, 4H), 3.97-4.01(m, 4H), 2.73-2.78 (m, 2H),
2.38 (s, 3H), 1.97-2.03 (m, 2H), 1.39 (s, 3H). 13C NMR (75.4 MHz, CDCl3): δ 141.1,
138.7, 138.3, 136.8, 129.5, 128.7, 127.0, 126.9, 109.7, 64.7, 40.9, 29.7, 23.9, 20.9.
ESI-MS m/z: 305.1506 [M+Na]+, calcd. for C19H22NaO2: 305.1517. IR (KBr, cm-1) : ν
2978, 2929, 2874, 1498, 1373, 1252, 1221, 1140, 1057, 862, 808.
4-(4-Methylphenyl)biphenyl.[12] (19) The product was made following method B
with a yield of 75% as a white solid. 1H NMR (300 MHz, CDCl3): δ 7.66 (s, 4H), 7.64
(d, J = 7.2 Hz, 2H), 7.54 (d, J = 8.1 Hz, 2H), 7.45(t, J = 7.5 Hz, 2H), 7.35(t, J = 7.5
Hz, 1H), 7.26 (d, J = 8.1 Hz, 2H), 2.40 (s, 3H). 13C NMR (75.4 MHz, CDCl3): δ 140.8,
140.1, 139.9, 137.8, 137.2, 129.6, 128.9, 127.5, 127.3, 127.1, 126.9, 21.0. MS (EI)
m/z: 244 (M+). IR (KBr, cm-1): ν 2918, 2849, 1633, 1485, 813, 760.
11

Byproduct of 3fc
3,3''-Dimethyl-p-terphenyl. The product was made following method B with a yield
of 17% as a white solid. 1H NMR (300 MHz, CDCl3): δ 7.65 (s, 4H), 7.4-.45 (m, 4H),
7.34 (t, J = 7.5 Hz, 2H), 7.17(d, J = 7.8 Hz, 2H), 2.42 (s, 6H). 13C NMR (75.4 MHz,
CDCl3): δ 140.8, 140.2, 138.5, 128.8, 128.1, 127.9, 127.5, 124.2, 21.5. MS (EI) m/z:
258 (M+). IR (KBr, cm-1): ν 3053, 1607, 1482, 1265, 909, 839, 781, 737.
12

Mechanism exploration
Eq S1
ESI MS spectroscopy of the monosulfate species
13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30