Microwave-Assisted Palladium-Catalyzed Arylation
Letters in Organic Chemistry, 2013, Vol. 10, No. 1 45
chromatography (petroleum ether/ethyl acetate = 4 : 1 – 10 :
1) to afford the corresponding coupling products.
13C NMR (100 MHz, CDCl3) ꢀ 144.0, 138.4, 137.5,
129.1, 128.3, 128.1, 127.7, 127.1, 126.4, 126.0, 17.4.
(E)-1,2-diphenylethene (3a)[13]
(E)-2-styrylpyridine (3i) [15]
1H NMR (400 MHz, CDCl3) ꢀ 7.51-7.53 (d, J = 8.0 Hz,
4H), 7.34-7.37 (t, J = 7.6 Hz, 4H), 7.24-7.28 (t, J = 8.0 Hz,
2H), 7.11 (s, 2H).
1H NMR (400 MHz, CDCl3) ꢀ 8.60-8.61 (d, J = 4.4 Hz,
1H), 7.57-7.68 (m, 4H), 7.36-7.40 (t, J = 8.4 Hz, 2H), 7.13-
7.31 (m, 4H).
13C NMR (100 MHz, CDCl3) ꢀ 137.5, 128.7, 127.6,
126.5.
13C NMR (100 MHz, CDCl3) ꢀ 155.4, 149.1, 136.9,
136.5, 133.3, 128.7, 128.6, 128.4, 127.3, 127.2, 122.1.
(E)-1-fluoro-4-styrylbenzene (3b)[14, 15]
(E)-oct-1-enylbenzene (3j) [16]
1H NMR (400 MHz, CDCl3) ꢀ 7.46-7.51 (m, 4H), 7.34-
1H NMR (400 MHz, CDCl3) ꢀ 7.17-7.39 (m, 5H), 6.35-
6.39 (d, J = 15.6 Hz, 1H), 6.19-6.26 (m, 1H), 2.18-1.23 (m,
2H), 1.23-1.34 (m, 8H), 0.88-0.91 (m, 3H).
7.38 (t, J = 7.2 Hz, 2H), 7.25-7.28 (m, 1H), 7.12 (m, 4H).
13C NMR (100 MHz, CDCl3) ꢀ 163.6, 161.1, 141.3,
128.7, 128.0, 127.9, 127.7, 127.45, 126.4, 115.7, 115.5.
13C NMR (100 MHz, CDCl3) ꢀ 138.0, 133.6, 128.3,
128.2, 128.1, 125.9, 33.1, 32.4, 29.0, 22.6, 22.1, 14.1.
(E)-1-chloro-4-styrylbenzene (3c) [15]
(E)-dodec-1-enylbenzene (3k) [18]
1H NMR (400 MHz, CDCl3) ꢀ 7.49-7.51 (d, J = 7.6 Hz,
2H), 7.43-7.45 (d, J = 8.0 Hz, 2H), 7.25-7.38 (m, 5H), 7.06
(s, 2H).
1H NMR (400 MHz, CDCl3) ꢀ 7.12-7.40 (m, 5H), 6.36-
6.40 (d, J = 16.0 Hz, 1H), 6.21-6.27 (m, 1H), 2.18-2.23 (m,
2H), 1.31(br s, 16H), 0.87-0.90 (m, 3H).
13C NMR (100 MHz, CDCl3) ꢀ 137.1, 136.0, 133.4,
129.4, 129.1, 128.1, 127.9, 127.6, 126.5.
13C NMR (100 MHz, CDCl3) ꢀ 137.8, 131.2, 129.5,
128.3, 126.6, 125.8, 33.1, 31.9, 29.6, 29.6, 29.5, 29.4, 29.3,
29.2, 22.7, 14.1.
(E)-1-bromo-4-styrylbenzene (3d) [15]
1H NMR (400 MHz, CDCl3) ꢀ 7.51-7.53 (d, J = 8.0 Hz,
4H), 7.34-7.37 (t, J = 7.6 Hz, 4H), 7.24-7.28 (t, J = 8.0 Hz,
2H), 7.11 (s, 2H).
(E)-tetradec-1-enylbenzene (3l) [19]
1H NMR (400 MHz, CDCl3) ꢀ 7.12-7.36 (m, 5H), 6.36-
6.40 (d, J = 16.0 Hz, 1H), 6.21-6.25 (m, 1H), 2.18-2.23 (m,
2H), 1.27 (br s, 20H), 0.87-0.90 (m, 3H).
13C NMR (100 MHz, CDCl3) ꢀ 137.0, 136.3, 131.7,
129.4, 128.7, 128.0, 127.9, 127.4, 126.5, 121.3.
13C NMR (100 MHz, CDCl3) ꢀ 138.0, 131.2, 129.7,
128.4, 127.0, 126.3, 33.0, 32.5, 31.9, 29.6, 29.6, 29.6, 29.5,
29.4,29.4, 29.3, 29.2, 22.7, 14.1.
(E)- ethyl 4-styrylbenzoate (3e) [15]
1H NMR (400 MHz, CDCl3); ꢀ 8.02-8.04 (d, J =8.0 Hz,
2H), 7.53-7.57 (m, 4H), 7.36-7.39 (m, 2H), 7.10-7.31 (m,
3H), 4.41 (q, J =6.8 Hz, 2H), 1.42 (m, 3H).
(E) -hexadec-1-enylbenzene (3m) [20]
1H NMR (400 MHz, CDCl3) ꢀ 7.12-7.37 (m, 5H), 6.35-
6.39 (d, J = 16.0 Hz, 1H), 6.21-6.26 (m, 1H), 2.18-2.23 (m,
2H), 1.27 (br s, 24H), 0.87-0.90 (m, 3H).
13C NMR (100 MHz, CDCl3) ꢀ166.4, 141.7, 136.7,
131.1, 129.9, 129.2, 128.7, 128.2, 127.6, 126.7, 126.2, 60.9,
14.3.
13C NMR (100 MHz, CDCl3) ꢀ 137.9, 131.2, 129.6,
128.4, 126.3, 125.9, 33.0, 32.5, 31.9, 29.7, 29.6, 29.5, 29.4,
29.3, 29.2, 22.7, 14.1.
(E)-1-methyl-4-styrylbenzene (3f) [15]
1H NMR (400 MHz, CDCl3) ꢀ 7.49-7.51 (d, J = 8.0 Hz,
2H), 7.41-7.43 (d, J = 8.0 Hz, 2H), 7.33-7.37 (m, 2H), 7.24-
7.26 (m, 1H), 7.14-7.16 (d, J = 8.0 Hz, 2H), 7.07-7.08(m,
2H), 2.37(s, 3H).
(E)-octadec-1-enylbenzene (3n)
1H NMR (400 MHz, CDCl3) ꢀ 7.12-7.35 (m, 5H), 6.35-
6.39 (d, J = 15.6 Hz, 1H), 6.21-6.26 (m, 1H), 2.17-2.23 (m,
2H), 1.27 (br s, 28H), 0.86-0.90 (m, 3H).
13C NMR(100MHz, CDCl3) ꢀ 137.8, 134.6, 129.4, 128.7,
128.6, 127.7, 127.4, 126.43, 126.40, 21.2.
13C NMR (100 MHz, CDCl3) ꢀ 137.9, 131.2, 129.6,
128.4, 126.7, 125.9, 33.0, 32.6, 31.9, 29.7, 29.6, 29.5, 29.4,
29.3,29.2, 22.7, 14.1.
HRMS-ESI: m/z [M+Na]+ calcd. for C24H40 Na
351.3028; found 351.3021.
(E)-1,3,5-trimethyl-2-styrylbenzene (3g) [16]
1H NMR (400 MHz, CDCl3) ꢀ 7.49-7.50 (d, J = 7.6 Hz,
2H), 7.35-7.38 (t, J = 7.2 Hz, 2H), 7.25-7.28 (d, J = 12.4 Hz,
1H), 7.08-7.12 (d, J = 16.8 Hz, 1H), 6.90 (s, 2H) 6.56-6.60
(d, J = 16.8 Hz, 1H), 2.34(s, 6H), 2.29(s, 3H).
13C NMR (100 MHz, CDCl3) ꢀ 137.7, 136.2, 136.1,
133.9, 133.6, 128.7, 128.6, 127.4, 126.9, 126.2, 21.0, 20.9.
CONCLUSION
In conclusion, a fast and high regioselective reaction has
been developed with olefins and diaryliodonium salts under
microwave irradiation without ligand and base. Diarylio-
donium salts 1 could perform the reaction with readily avail-
able styrenes and alkenes by 2 mol% of Pd(OAc)2 in 60 sec-
onds, assembling olefins in up to 99% yields with excellent
(E)-prop-1-ene-1,2-diyldibenzene (3h) [17]
1H NMR (400 MHz, CDCl3) ꢀ 7.54-7.56 (d, J = 7.6 Hz,
2H), 7.45-7.47 (d, J = 8.0 Hz, 1H), 7.39-7.41 (m, 3H), 7.27-
7.33 (m, 3H), 6.86(s, 2H), 2.31(s, 3H).