Please do not adjust margins
New Journal of Chemistry
Page 3 of 10
DOI: 10.1039/C7NJ04629D
Journal Name
ARTICLE
103.0, 103.3, 106.8, 110.5, 113.8, 116.5, 119.7, 121.0, 121.5, temperature, diluted with dichloromethane, washed with
122.8, 123.3, 123.6, 123.7, 138.5, 138.8, 139.2, 139.6, 140.3, water and brine. The organic layer was dried over anhydrous
140.9. HR-MS (MALDI): m/z [M]+ calcd for C53H71N3Si, Na2SO4 and concentrated in vacuum. The residue was purified
777.5417; found, 777.5418.
by
column
chromatography
using
petroleum
2.3.4. Synthesis of compound 5. To a 100 mL round bottom ether/dichloromethane (3:1) as the eluent to give compound
7
1
4 (330 mg, 0.42 mmol) in (78% yield), a pale yellow oil. H NMR (400 MHz, CDCl3) δ 0.84
flask with the solution of compound
30 mL dry THF, TBAF (329 mg, 1.26 mmol) were added. After – 0.95 (m, 9H), 1.16 – 1.44 (m, 30H), 1.51 (s, 12H), 1.94 – 2.14
stirring at room temperature for half an hour, the mixture was (m, 6H), 4.90 – 4.96 (m, 4H), 5.01 – 5.07 (t, J = 7.8 Hz, 2H), 7.34
diluted with dichloromethane, washed with water and brine. – 7.43 (q, J = 7.3 Hz, 2H), 7.45 – 7.54 (t, J = 7.6 Hz, 2H), 7.63 –
The organic layer was dried over anhydrous Na2SO4 and 7.69 (d, J = 8.1 Hz, 2H), 7.84 – 7.94 (d, J = 8.0 Hz, 1H), 8.18 (s,
concentrated in vacuum. The crude product was transferred 1H), 8.29 – 8.38 (t, J = 8.7 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ
into a 100 mL two-neck round bottom flask, and compound 10 14.1, 22.6, 24.9, 26.5, 26.9, 29.1, 29.7, 29.9, 31.7, 46.9, 83.7,
(219 mg, 0.63 mmol), AsPh3 (257 mg, 0.84 mmol), Pd2(dba)3 103.1, 110.5, 116.9, 119.7, 120.7, 121.4, 121.6, 122.7, 123.3,
(77 mg, 0.08 mmol), 15 mL THF, and 15 mL NEt3 were 123.5, 125.9, 138.8, 139.3, 139.6, 140.5, 140.9. HR-MS
successively added into the flask. The mixture was heated at (MALDI): m/z [M]+ calcd for C54H74BN3O2, 807.5874, found,
60 °C overnight under nitrogen, then cooled to room 807.5878.
temperature and diluted with dichloromethane, washed with
2.3.7. Synthesis of compound 8. In a 100 mL round bottom
(260 mg, 0.32 mmol), compound 10 (93 mg,
water and brine. The organic layer was dried over anhydrous flask, compound
7
Na2SO4 and concentrated in vacuum. The residue was purified 0.27 mmol), Pd(PPh3)4 (35 mg, 0.03 mmol) were dissolved in
by column chromatography using dichloromethane as the 20 mL THF and 5 mL K2CO3 (2 M). The mixture was heated at
eluent to give compound
5 (55% yield, two steps), a red solid. 60 °C for 8 h under nitrogen, then cooled to room
1H NMR (400 MHz, CDCl3) δ 0.78 – 0.89 (m, 9H), 1.10 – 1.38 (m, temperature, diluted with dichloromethane, washed with
30H), 1.86 – 2.10 (t, J = 8.2 Hz, 6H), 3.98 (s, 3H), 4.79 – 5.01 (m, water and brine. The organic layer was dried over anhydrous
6H), 7.31 – 7.38 (td, J = 7.6, 2.6 Hz, 2H), 7.43 – 7.49 (t, J = 7.5 Na2SO4 and concentrated in vacuum. The residue was purified
Hz, 2H), 7.49 – 7.55 (dd, J = 8.1, 6.5 Hz, 1H), 7.60 – 7.67 (m, by
column
chromatography
using
petroleum
3H), 7.70 – 7.77 (m, 2H), 7.91 (s, 1H), 8.03 – 8.09 (m, 2H), 8.18 ether/dichloromethane (1:1) as the eluent to give compound
8
– 8.23 (m, 2H), 8.24 – 8.29 (dd, J = 10.0, 2.9 Hz, 2H).13C NMR (90% yield), a red solid. 1H NMR (400 MHz, CDCl3) δ 0.73 – 0.91
(100 MHz, CDCl3) δ 14.1, 22.5, 26.6, 29.2, 29.8, 31.7, 47.0, (m, 9H), 1.08 – 1.42 (m, 30H), 1.93 – 2.16 (m, 6H), 3.99 (s, 3H),
52.2, 84.9, 98.7, 103.0, 103.2, 103.4, 110.5, 113.8, 115.9, 4.84 – 5.05 (m, 6H), 7.31 – 7.39 (t, J = 7.7 Hz, 2H), 7.43 – 7.51
117.4, 119.8, 121.2, 121.5, 122.9, 123.3, 123.8, 124.1, 128.3, (d, J = 7.7 Hz, 2H), 7.61 – 7.68 (d, J = 8.2 Hz, 2H), 7.84 – 7.92 (t,
129.1, 129.4, 129.8, 131.5, 132.2, 132.4, 132.7, 138.5, 139.3, J = 8.2 Hz, 2H), 7.93 – 7.99 (d, J = 7.6 Hz, 1H), 8.07 – 8.13 (d, J =
139.8, 140.4, 140.9, 141.3, 152.9, 155.3, 166.8. HR-MS 8.0 Hz, 2H), 8.20 – 8.26 (d, J = 8.1 Hz, 2H), 8.27 – 8.33 (t, J = 7.5
(MALDI): m/z [M]+ calcd for C64H71N5O2S, 973.5328, found, Hz, 2H), 8.35 – 8.41 (d, J = 7.6 Hz, 2H). 13C NMR (100 MHz,
973.5325.
2.3.5. Synthesis of compound 6. The compound
synthesized using the same procedure for compound
CDCl3) δ 14.1, 22.6, 26.7, 29.1, 29.7, 31.7, 46.9, 52.2, 103.1,
6
was 110.4, 111.8, 119.7, 120.7, 121.5, 122.8, 123.3, 123.4, 123.7,
5
except 128.4, 128.6, 128.8, 129.1, 129.6, 129.8, 131.2, 131.3, 131.5,
replacing compound 10 with compound 11. The residue was 132.2, 132.3, 134.8, 138.7, 139.2, 139.8, 140.8, 140.9, 141.2,
purified by column chromatography using dichloromethane as 141.9, 154.0, 154.4, 166.9. HR-MS (MALDI): m/z [M]+ calcd for
the eluent to give compound
solid. 1H NMR (400 MHz, CDCl3) δ 0.80 – 0.88 (m, 9H), 1.17 –
1.33 (m, 30H), 1.94 – 2.06 (m, 6H), 4.84 – 4.96 (m, 6H), 7.32 – synthesized according to the same procedure for compound
6
(52% yield, two steps), a red C62H71N5O2S, 949.5328, found, 949.5325.
2.3.8. Synthesis of compound 9. The compound
9
was
8
7.37 (t, J = 7.3 Hz, 2H), 7.44 – 7.51 (t, J = 7.6 Hz, 2H), 7.61 – except using compound 11 instead of compound 10. The
7.66 (m, 3H), 7.71 – 7.74 (d, J = 7.2 Hz, 1H), 7.88 – 7.91 (d, J = residue was purified by column chromatography using
5.1 Hz, 2H), 7.99 – 8.03 (d, J = 7.7 Hz, 2H), 8.11 – 8.15 (d, J = 7.6 dichloromethane as the eluent to give compound 6 (84%
Hz, 2H), 8.21 – 8.30 (dd, J = 12.8, 8.4 Hz, 3H), 10.09 (s, 1H). 13 yield), a red solid. 1H NMR (400 MHz, CDCl3) δ 0.79 – 0.91 (m,
C
NMR (100 MHz, CDCl3) δ 14.0, 22.6, 26.6, 29.1, 29.7, 31.7, 9H), 1.10 – 1.36 (m, 30H), 1.89 – 2.11 (q, J = 7.8 Hz, 6H), 4.78 –
47.0, 84.9, 99.0, 103.0, 103.2, 103.4, 110.5, 110.6, 113.8, 5.00 (m, 6H), 7.31 – 7.39 (t, J = 7.6 Hz, 2H), 7.43 – 7.51 (t, J =
115.8, 117.7, 119.8, 121.2, 121.5, 122.9, 123.3, 123.8, 124.1, 7.7 Hz, 2H), 7.59 – 7.67 (m, 3H), 7.69 – 7.76 (d, J = 7.3 Hz, 1H),
128.4, 129.7, 129.9, 132.3, 135.8, 138.5, 139.3, 139.8, 140.4, 7.86 – 7.93 (d, J = 5.7 Hz, 2H), 7.97 – 8.06 (d, J = 7.8 Hz, 2H),
140.9, 142.8, 152.8, 155.3, 191.8. HR-MS (MALDI): m/z [M]+ 8.09 – 8.16 (d, J = 7.8 Hz, 2H), 8.20 – 8.30 (dd, J = 13.1, 8.1 Hz,
calcd for C63H69N5OS, 943.5223, found, 943.5220.
2.3.6. Synthesis of compound 7. In a 100 mL two-neck 29.1, 29.9, 31.7, 46.9, 102.9, 103.1, 103.2, 110.4, 110.5, 111.8,
round bottom flask, compound (500 mg, 0.66 mmol), 119.7, 120.6, 121.4, 121.5, 122.8, 123.3, 123.8, 127.5, 129.0,
3H), 10.09 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 14.1, 22.6, 26.6,
3
bis(pinacolato)diboron (335mg, 1.32 mmol), potassium acetate 129.7, 129.9, 130.7, 131.1, 135.0, 135.6, 138.7, 139.1, 139.8,
(206mg, 2.10 mmol), Pd(dppf)Cl2 (57mg, 0.07 mmol) were 140.8, 140.9, 141.1, 143.4, 153.9, 154.3, 191.9. HR-MS
dissolved in 30 mL 1,4-dioxane. The mixture was heated at 90 (MALDI): m/z [M]+ calcd for C61H69N5OS, 919.5223, found,
°C overnight under nitrogen, then cooled to room 919.5220.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins