Synthesis of diarylmethanes through palladium-catalyzed coupling of benzylic phosphates with arylsilanes

Article abstract of DOI:10.1055/s-0034-1379366

An efficient approach to the benzylation of arenes has been developed. The reactions described provide straightforward access to diarylmethanes through Pd-catalyzed coupling of benzylic phosphates with arylsilanes in good to excellent yields. The reaction tolerates a wide range of functionalities such as halide, alkoxyl, and nitro groups.

Full text of DOI:10.1055/s-0034-1379366

Accounts and
Rapid Communications in
Synthetic Organic Chemistry
SUPPORTING INFORMATION
6<1/(77
Supporting Information
for DOI: 10.1055/s-0034-1379366
© Georg Thieme Verlag KG Stuttgart · New York 2014
Thieme

Supporting Information
for
Synthesis of Diarylmethanes WKURXJK PDOODGLXP-Catalyzed Coupling
of %HQ]\OLFꢀ3KRVSKDWHVꢀZLWKꢀ$U\OVLODQHV
Pengbo Zhang,a Jian Xu,a Yuzhen Gao,a Xueqin Li,a Guo Tang,*a Yufen Zhaoa,b
a
College of Chemistry and Chemical Engineering and the Key Laboratory for Chemical Biology of
Fujian Province, Xiamen University, Xiamen 361005, P. R. China. Tel. & Fax: +86-592-2185780;
E-mail: t12g21@xmu.edu.cn
b Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education),
Department of Chemistry, Tsinghua University, Beijing 100084,China
Spectroscopic and Analytical Data
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1H NMR and 13C NMR Spectra of all compounds
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1
Diphenylmethane (3aa) (CAS no: 101-81-5). Colorless oil. H NMR (400 MHz,
CDCl3) δ 7.30 - 7.24 (m, 4H), 7.20 – 7.14 (m, 6H), 3.96 (s, 2H). 13C NMR (100 MHz,
CDCl3) δ 141.5, 129.1, 128.7, 126.3, 42.3.
1-Benzyl-2-methylbenzene (3ba) (CAS no: 713-36-0). Colorless oil. 1H NMR (400
MHz, CDCl3) δ 7.27 - 7.21 (m, 2H), 7.20 – 7.05 (m, 7H), 3.96 (s, 2H), 2.22 (s, 3H).
13C NMR (100 MHz, CDCl3) δ 140.63, 139.13, 136.81, 130.49, 130.17, 128.95,
128.59, 126.66, 126.19, 126.12, 39.67, 19.83.
1-Benzyl-3-methylbenzene (3ca) (CAS no: 620-47-3). Colorless oil. 1H NMR (400
MHz, CDCl3) δ 7.27 - 7.24 (m, 2H), 7.18 – 7.12 (m, 4H), 6.99 – 6.96 (m, 3H), 3.92 (s,
2H), 2.29 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 141.42, 141.21, 138.19, 129.90,
129.10, 128.62, 128.53, 127.01, 126.19, 126.17, 42.07, 21.59.
1-Benzyl-3-methylbenzene (3da) (CAS no: 620-83-7). Colorless oil. 1H NMR (400
MHz, CDCl3) δ 7.30 - 7.20 (m, 2H), 7.20 – 7.10 (m, 3H), 7.08 – 7.03 (s, 4H), 3.92 (s,
13
2H), 2.29 (s, 3H). C NMR (100 MHz, CDCl3) δ 141.6, 138.3, 135.7, 129.3, 129.1,
129.0, 128.6, 126.1, 41.7, 21.2.
1
1-Benzylnaphthalene (3ea) (CAS no: 611-45-0). White solid. H NMR (400 MHz,
CDCl3) δ 7.99 - 7.96 (m, 1H), 7.85 – 7.83 (m, 1H), 7.75 – 7.73 (d, J = 8.14 Hz, 1H),
7.45 - 7.38 (m, 3H), 7.28 – 7.15 (m, 6H), 4.43 (s, 2H). 13C NMR (100 MHz, CDCl3) δ
140.84, 136.84, 134.16, 132.36, 128.95, 128.87, 128.65, 127.54, 127.36, 126.26,
126.17, 125.76, 124.48, 39.24.
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1
2-Benzylnaphthalene (3fa) (CAS no: 613-59-2). White solid. H NMR (400 MHz,
CDCl3) δ 7.78 - 7.72 (m, 3H), 7.61 (s, 1H), 7.44 – 7.38 (m, 2H), 7.30 – 7.25 (m, 3H),
13
7.22 – 7.17 (m, 3H), 4.12 (s, 2H). C NMR (100 MHz, CDCl3) δ 141.19, 138.82,
133.87, 132.35, 129.25, 128.71, 128.29, 128.85, 127.77, 127.32, 126.37, 126.18,
125.55, 42.34.
1-Benzyl-4-tert-butylbenzene (3ga) (CAS no: 16251-99-3). Colorless oil. 1H NMR
(400 MHz, CDCl3) δ 7.30 - 7.24 (m, 4H), 7.19 – 7.09 (m, 5H), 3.93 (s, 2H), 1.29 (s,
13
9H). C NMR (100 MHz, CDCl3) δ 149.01, 141.48, 138.28, 129.17, 128.72, 128.63,
126.19, 125.55, 41.65, 34.56, 31.61.
1
1-Benzyl-4-phenylbenzene (3ha) (CAS no: 613-42-3). White solid. H NMR (400
MHz, CDCl3) δ 7.57 - 7.49 (m, 4H), 7.42 – 7.38 (m, 2H), 7.33 – 7.20 (m, 8H), 4.01 (s,
2H). 13C NMR (100 MHz, CDCl3) δ 141.22, 140.46, 139.26, 129.53, 129.18, 128.92,
128.73, 127.42, 127.28, 127.22, 126.36, 41.80.
1-Benzyl-4-methoxybenzene (3ia) (CAS no: 834-14-0). Colorless oil. 1H NMR (400
MHz, CDCl3) δ 7.28 – 7.23 (m, 2H), 7.18 – 7.14 (m, 3H), 7.09 – 7.07 (m, 2H), 6.82 –
6.80 (m, 2H), 3.90 (s, 2H), 3.74 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 158.15,
141.76, 133.42, 130.04, 128.99, 128.60, 126.15, 114.05, 55.38, 42.21.
1-Benzyl-4-fluorobenzene (3ja) (CAS no: 587-79-1). Colorless oil. 1H NMR (400
MHz, CDCl3) δ 7.30 - 7.25 (m, 2H), 7.22 – 7.10 (m, 5H), 6.98 – 6.92 (m, 2H), 3.93 (s,
13
2H). C NMR (100 MHz, CDCl3) δ 161.61 (d, J = 246.41 Hz ), 141.14 (d, J = 0.87
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Hz), 136.97 (d, J = 3.38 Hz), 130.48 (d, J = 8.16 Hz), 129.03, 128.74, 126.41, 115.40
(d, J = 21.44 Hz), 41.27.
1-Benzyl-3-fluorobenzene (3ka) (CAS no: 587-79-1). Colorless oil. 1H NMR (400
MHz, CDCl3) δ 7.31 – 7.24 (m, 2H), 7.24 – 7.13 (m, 4H), 6.97 – 6.92 (m, 1H), 6.91 –
6.83 (m, 2H), 3.94 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 163.20 (d, J = 245.55 Hz),
143.90 (d, J = 7.89 Hz), 140.49, 130.02 (d, J =8.02 Hz), 129.13, 128.79, 126.55,
124.74 (d, J =2.89 Hz), 115.95 (d, J =21.17 Hz), 113.17 (d, J =21.16 Hz), 41.83 (d, J
=1.36 Hz).
1-Benzyl-4-chlorobenzene (3la) (CAS no: 831-81-2). Colorless oil. 1H NMR (400
MHz, CDCl3) δ 7.34 - 7.18 (m, 5H), 7.16 – 7.11 (m, 2H), 7.10 – 7.07 (m, 2H), 3.93 (s,
13
2H). C NMR (100 MHz, CDCl3) δ 140.75, 139.79, 132.11, 130.45, 129.06, 128.77,
127.36, 126.49, 41.44.
1-Benzyl-4-(trifluoromethyl)benzene (3ma) (CAS no: 34239-04-8 ). Colorless oil. 1H
NMR (400 MHz, CDCl3) δ 7.56 – 7.49 (m, 2H), 7.33 – 7.25 (m, 4H), 7.25 – 7.19 (m,
1H), 7.19 – 7.14 (m, 2H), 4.02 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 145.44, 140.20,
129.41, 128.89, 128.88, 128.49 (q, J =33.41 Hz), 126.69, 125.60 (q, J =4.01 Hz),
124.46 (q, J =272.46 Hz), 41.92.
1-Benzyl-3-(trifluoromethyl)benzene (
) (CAS no: 75198-32-2 ). Colorless oil. 1H
3na
NMR (400 MHz, CDCl3) δ 7.48 – 7.41 (m, 2H), 7.40 – 7.26 (m, 4H), 7.23 – 7.14 (m,
3H), 4.01 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 142.25, 140.23, 132.52, 131.01 (q,
J =32.31 Hz ), 129.12, 129.11, 129.09, 128.89, 126.69, 125.80 (q, J =3.88 Hz), 124.51
(q, J = 272.54 Hz), 123.25 (q, J =3.87 Hz), 41.90.
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1-Benzyl-3-nitrobenzene (3oa) (CAS no: 5840-41-5). Colorless oil. 1H NMR (400
MHz, CDCl3) δ 8.07 – 8.04 (m, 2H), 7.52 – 7.42 (m, 2H), 7.34 – 7.17 (m, 5H), 4.08 (s,
13
2H). C NMR (100 MHz, CDCl3) δ 148.59, 143.39, 139.56, 135.29, 129.54, 129.10,
129.02, 126.93, 123.89, 121.54, 41.69.
1
(E)-prop-1-ene-1,3-diyldibenzene (3qa) (CAS no: 3412-44-0). Colorless oil. H
NMR (400 MHz, CDCl3) δ 7.36 – 7.18 (m, 10H), 6.45 (d, J =15.90 Hz, 1H), 6.35 (m,
1H), 3.54 (d, J = 6.51 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 140.39, 137.71,
131.30, 129.45, 128.88, 128.71, 127.31, 126.61, 126.39, 126.35, 39.56.
1
Triphenylmethane (3ra) (CAS no: 519-73-3). White solid. H NMR (400 MHz,
CDCl3) δ 7.30 - 7.24 (m, 6 H), 7.21 – 7.18 (m, 3 H), 7.14 – 7.07 (m, 6H), 5.54 (s, 2H).
13C NMR (100 MHz, CDCl3) δ 144.11, 129.66, 128.50, 126.49, 57.06.
1-Methyl-3-(4-methylbenzyl)benzene (3cb) (CAS no: 21895-16-9) Colorless oil. 1H
NMR (400 MHz, CDCl3) δ 7.17 - 7.12 (m, 1H), 7.10 – 7.03 (m, 4H), 6.99 – 6.965 (m,
3H), 3.88 (s, 2H), 2.29 (s, 3H), 2.28 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 141.52,
138.40, 138.16, 135.64, 129.85, 129.32, 128.99, 128.51, 126.94, 126.12, 41.66, 21.59,
21.20.
1-Fluoro-3-(4-methylbenzyl)benzene (3kb) (CAS no: 1352918-73-0) Colorless oil. 1H
NMR (400 MHz, CDCl3) δ 7.23 – 7.16 (m, 1H), 7.10 – 7.03 (m, 4H), 6.94 (d, J = 7.37
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Hz, 2H), 6.87 – 6.83 (m, 2H), 3.90 (s, 2H), 2.30 (s, 3H). 13C NMR (100 MHz, CDCl3)
δ 163.17 (d, J = 245.35 Hz), 144.21 (d, J = 7.19 Hz), 137.45, 136.05, 129.98 (d, J =
8.55 Hz), 129.47, 129.01, 124.65 (d, J = 2.72 Hz), 115.90 (d, J = 20.99 Hz), 113.07(d,
J = 20.97 Hz), 41.41 (d, J = 1.57 Hz), 21.20.
1-(4-Methylbenzyl)-3-(trifluoromethyl)benzene (3nb) (CAS no: 1621007-08-6).
Colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.51 – 7.49 (m, 2H), 7.45 – 7.40 (m, 2H),
7.19 – 7.11 (m, 4H), 4.04 (s, 2H), 2.38 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 142.55,
137.19, 136.22, 132.46, 130.94 (q, J =31.91 Hz ), 129.57, 129.06, 128.99, 125.72 (q,
J =3.80 Hz), 124.45 (q, J = 272.25 Hz), 123.14 (q, J =3.80 Hz), 41.48, 21.89.
Allylbenzene (3ac) (CAS no: 300-57-2) Colorless oil. 1H NMR (400 MHz, CDCl3) δ
7.33 – 7.30 (m, 2H), 7.26 – 7.20 (m, 3H), 6.04 – 5.96 (m, 1H), 5.13 – 5.08 ( m, 2H),
3.42 (d, J =6.67 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 140.26, 137.67, 128.79,
128.62, 126.27, 115.99, 40.46.
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