PCCP
Paper
132.46, 132.18, 130.65, 130.23, 129.62, 127.70, 123.95, 121.48, (m, 4H), 1.41–1.32 (m, 10H), 0.90 (s, 9H), 0.06 (s, 6H). 13C-NMR
119.67, 119.04, 114.49, 111.03, 68.50, 64.14, 32.72, 29.67, 29.62, (100 MHz, CDCl3) d = 165.00, 163.87, 151.74, 145.04, 136.85,
29.49, 29.24, 27.02, 26.13, 25.91, 20.61, 19.37. ESI-MS (CH3OH/ 132.80, 132.50, 128.50, 127.85, 122.72, 121.35, 119.04, 114.52,
formic acid 0.01%, soft pos. mode): m/z calcd for C47H55NO5Si 111.15, 68.52, 63.47, 33.03, 29.70, 29.64, 29.57, 29.49, 29.24,
[M + H2O]+ 741.4, found 741.8, C47H54NO4Si [M + H]+ 724.4, 26.14, 25.95, 18.54, ꢀ5.10. Elem. anal. calcd for C36H47NO4Siꢂ
found 724.5, C41H48NO4Si [M–Ph]+ 646.4, found 646.8. Elem. 0.01CH2Cl2 (586.70 g molꢀ1): C 73.74, H 8.19, N 2.39; found:
anal. calcd for C47H53NO4Siꢂ0.07CH2Cl2 (729.96 g molꢀ1): C 73.74, H 8.19, N 2.28.
C 77.45, H 7.34, N 1.92; found: C 77.44, H 7.47, N 1.77.
TBDMSO-C10H20-LC30,0. White solid (Z = 93%). 1H-NMR
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TBDPSO-C10H20-LC00,3. Colorless wax (Z = 98%). 1H-NMR (400 MHz, CDCl3) d = 8.18 (d, J = 8.9 Hz, 2H), 7.73 and 7.68
(400 MHz, CDCl3) d = 8.16 (d, 3J = 8.8 Hz, 2H), 7.68 (d, 3J = (2d, AB system, 3J = 8.6, 4H), 7.49 (m, 1H), 7.46 (m, 1H), 7.25 (d,
7.8 Hz, 4H), 7.63 (d, 3J = 8.6 Hz, 2H), 7.54 (m, 1H), 7.49 3J = 8.0 Hz, 1H), 7.00 (d, 3J = 8.9 Hz, 2H), 4.06 (t, 3J = 6.6 Hz, 2H),
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(dd, J = 8.0 Hz and J = 1.7 Hz, 1H), 7.42–7.36 (m, 6H), 7.32 3.61 (t, J = 6.6 Hz, 2H), 2.31 (s, 3H), 1.87–1.80 (m, 2H), 1.55–
(d, 3J = 8.6 Hz, 2H), 6.99 (d, 3J = 8.8 Hz, 2H), 4.06 (t, 3J = 6.5 Hz, 1.45 (m, 4H), 1.39–1.32 (m, 10H), 0.90 (s, 9H), 0.06 (s, 6H).
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2H), 3.67 (t, J = 6.5 Hz, 2H), 2.63 (s, 3H), 1.87–1.80 (m, 2H), 13C-NMR (100 MHz, CDCl3) d = 164.71, 163.86, 150.36, 145.24,
1.60–1.54 (m, 2H), 1.53–1.45 (m, 2H), 1.40–1.29 (m, 10H), 1.06 137.05, 132.72, 132.48, 131.46, 130.17, 127.84, 125.99, 123.06,
(s, 9H). 13C-NMR (100 MHz, CDCl3) d = 165.01, 163.85, 151.62, 121.27, 119.08, 114.54, 111.00, 68.51, 63.46, 33.02, 29.69, 29.63,
144.89, 142.58, 137.05, 135.73, 134.34, 133.14, 132.50, 129.63, 29.56, 29.48, 29.23, 26.13, 25.94, 18.53, 16.61, ꢀ5.10. Elem.
128.98, 128.48, 127.71, 125.10, 122.62, 121.39, 118.37, 114.51, anal. calcd for C37H49NO4Si (599.87 g molꢀ1): C 74.08, H 8.23,
111.57, 68.52, 64.14, 32.72, 29.67, 29.63, 29.49, 29.24, 27.02, N 2.33; found: C 73.96, H 8.38, N 2.20.
26.13, 25.91, 20.82, 19.38. ESI-MS (CH3OH/formic acid
0.01%, soft pos. mode): m/z calcd for C47H55NO5Si [M + H2O]+ (400 MHz, CDCl3) d = 8.15 (d, J = 8.7 Hz, 2H), 7.72 (d, J = 8.0
TBDMSO-C10H20-LC20,0. White solid (Z = 96%). 1H-NMR
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741.4, found 741.7, C47H54NO4Si [M + H]+ 724.4, found 724.5, Hz, 2H), 7.45 (d, J = 7.9 Hz, 2H), 7.24 (d, J = 8.1 Hz, 1H), 7.15
C
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41H48NO4Si [M–Ph]+ 646.4, found 646.8. Elem. anal. calcd for (m, 1H), 7.12 (m, 1H), 6.99 (d, 3J = 8.7 Hz, 2H), 4.05 (t, 3J = 6.5 Hz,
47H53NO4Siꢂ0.05CH2Cl2 (728.26 g molꢀ1): C 77.60, H 7.35, 2H), 3.61 (t, 3J = 6.6 Hz, 2H), 2.28 (s, 3H), 1.86–1.80 (m, 2H), 1.56–
N 1.92; found: C 77.57, H 7.43, N 1.77.
1.45 (m, 4H), 1.39–1.32 (m, 10H), 0.90 (s, 9H), 0.05 (s, 6H). 13C-NMR
TBDPSO-C10H20-LC20,2. Colorless oil (Z = 98%). 1H-NMR (100 MHz, CDCl3) d = 165.19, 163.81, 151.05, 146.21, 137.67, 136.90,
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(400 MHz, CDCl3) d = 8.16 (d, J = 8.8 Hz, 2H), 7.68 (m, 4H), 132.46, 132.18, 130.65, 130.23, 123.95, 121.48, 119.67, 119.04,
7.59 (m, 1H), 7.54 (dd, 3J = 7.8 Hz and 4J = 1.7 Hz, 1H), 7.45–7.36 114.49, 111.03, 68.50, 63.47, 33.03, 29.70, 29.64, 29.57, 29.50,
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(m, 7H), 7.25 (d, J = 7.9 Hz, 1H), 7.16 (d, J = 2.1 Hz, 1H), 7.11 29.24, 26.14, 25.95, 20.61, 18.53, ꢀ5.10. Elem. anal. calcd for
(m, 1H), 6.99 (d, J = 8.9 Hz, 2H), 4.06 (t, J = 6.5 Hz, 2H), 3.67 C37H49NO4Siꢂ0.03CH2Cl2 (602.42 g molꢀ1): C 73.83, H 8.21,
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(t, 3J = 6.5 Hz, 2H), 2.13 (s, 3H), 2.06 (s, 3H), 1.87–1.80 (m, 2H), N 2.33; found: C 73.88, H 8.34, N 2.20.
1.61–1.54 (m, 2H), 1.52–1.45 (m, 2H), 1.41–1.30 (m, 10H), 1.06
TBDMSO-C10H20-LC00,3. White solid (Z = 94%). 1H-NMR
(s, 9H). 13C-NMR (100 MHz, CDCl3) d = 165.13, 163.76, 150.80, (400 MHz, CDCl3) d = 8.16 (d, 3J = 8.9 Hz, 2H), 7.68 (d, 3J =
146.02, 137.88, 137.21, 137.04, 135.70, 134.31, 133.57, 132.42, 8.0 Hz, 1H), 7.63 (d, 3J = 8.6 Hz, 2H), 7.54 (m, 1H), 7.49 (m, 1H),
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130.52, 129.74, 129.61, 129.58, 127.69, 123.46, 121.53, 119.41, 7.32 (d, J = 8.6 Hz, 2H), 6.99 (d, J = 8.9 Hz, 2H), 4.06 (t, J =
119.13, 114.48, 111.41, 68.48, 64.12, 32.70, 29.65, 29.61, 29.47, 6.6 Hz, 2H), 3.61 (t, 3J = 6.6 Hz, 2H), 2.62 (s, 3H), 1.87–1.80
29.23, 27.01, 26.12, 25.89, 19.96, 19.86, 19.35. ESI-MS (CH3OH/ (m, 2H), 1.56–1.45 (m, 4H), 1.39–1.32 (m, 10H), 0.90 (s, 9H),
formic acid 0.01%, soft pos. mode): m/z calcd for C48H57NO5Si 0.06 (s, 6H). 13C-NMR (100 MHz, CDCl3) d = 165.01, 163.85,
[M + H2O]+ 755.4, found 755.7, C48H56NO4Si [M + H]+ 738.4, 151.63, 144.89, 142.57, 137.05, 133.14, 132.49, 128.98, 128.47,
found 738.9, C42H50NO4Si [M–Ph]+ 660.4, found 660.5. Elem. 125.10, 122.62, 121.38, 118.37, 114.51, 111.57, 68.51, 63.47,
anal. calcd for C48H55NO4Siꢂ0.01CH2Cl2 (738.89 g molꢀ1): 33.03, 29.70, 29.64, 29.57, 29.50, 29.24, 26.14, 25.95, 20.81,
C 78.01, H 7.55, N 1.90; found: C 78.01, H 7.55, N 1.74.
18.54, ꢀ5.10. Elem. anal. calcd for C37H49NO4Siꢂ0.04CH2Cl2
(603.27 g molꢀ1): C 73.74, H 8.20, N 2.32; found: C 73.79,
H 8.35, N 2.19.
General procedure for the preparation of TBDMSO-C10H20-LCi0, j
To a solution of OCBi0, j (1 eq.), 6 (1.1 eq.) and DPTS (1 eq.) in dry
TBDMSO-C10H20-LC20,2. Pale yellow oil (Z = 99%). 1H-NMR
CH2Cl2 (25 mL) stirred at 0 1C were added DCC (1.5 eq.) and (400 MHz, CDCl3) d = 8.16 (d, 3J = 8.7 Hz, 2H), 7.58 (m, 1H), 7.54
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4-ppy (spatula tip). The mixture was allowed to heat slowly (m, 1H), 7.24 (d, J = 7.8 Hz, 1H), 7.16 (m, 1H), 7.10 (m, 2H),
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to room temperature and stirred for 48 h. After filtration, 6.99 (d, J = 8.5 Hz, 2H), 4.06 (t, J = 6.5 Hz, 2H), 3.61 (t, J =
the solution was evaporated to dryness and the residue was 6.6 Hz, 2H), 2.13 (s, 3H), 2.06 (s, 3H), 1.87–1.80 (m, 2H), 1.55–
purified by column chromatography (SiO2, CH2Cl2) to afford 1.45 (m, 4H), 1.41–1.32 (m, 10H), 0.90 (s, 9H), 0.06 (s, 6H).
pure TBDMSO-C10H20-LCi0, j. Yields ranged from 93 to 99%.
13C-NMR (100 MHz, CDCl3) d = 165.15, 163.78, 150.82, 146.04,
TBDMSO-C10H20-LC00,0. White solid (Z = 99%). 1H-NMR 137.90, 137.23, 137.06, 133.58, 132.43, 130.54, 129.76, 129.60, 123.48,
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(400 MHz, CDCl3) d = 8.16 (d, J = 8.9 Hz, 2H), 7.74 and 7.69 121.56, 119.43, 119.15, 114.49, 111.44, 68.50, 63.46, 33.02, 29.69,
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(2d, AB system, J = 8.7 Hz, 4H), 7.64 (d, J = 8.6 Hz, 2H), 7.33 29.64, 29.57, 29.49, 29.24, 26.14, 25.94, 19.98, 19.87, 18.53, ꢀ5.10.
(d, 3J = 8.6 Hz, 2H), 6.99 (d, 3J = 8.9 Hz, 2H), 4.06 (t, 3J = 6.5 Hz, Elem. anal. calcd for C38H51NO4Siꢂ0.02CH2Cl2 (615.60 g molꢀ1):
2H), 3.61 (t, 3J = 6.6 Hz, 2H), 1.87–1.80 (m, 2H), 1.55–1.45 C 74.18, H 8.36, N 2.28; found: C 74.17, H 8.50, N 2.10.
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