J.-L. Lv et al. / Tetrahedron 67 (2011) 9080e9086
9085
(0.92 equiv), and the detritylated residue was purified by silica gel
column chromatography using EtOAc as eluent to give CBzABzTD2
(1.51 g, 78% yield for two steps) as white foam. 1H NMR (300 MHz,
mixture solvent of ethane-1,2-diamine/ethanol (1:1) and stirred at
55 ꢁC for 50 min. After the solvent was removed, the residue was
purified by silica gel column chromatography using EtOAc as eluent
to give A2D2 (0.74 g, 29% yield for three steps) as white foam. 1H
acetone-d6)
d 10.09 (br s, 1H), 8.62 (s, 1H), 8.44 (s, 1H), 8.37 (d,
J¼7.5 Hz, 1H), 8.14e8.11 (m, 4H), 7.63e7.29 (m, 28H), 6.73e6.48 (m,
10H), 6.34e6.22 (m, 2H), 5.08e5.03 (m, 13H), 4.88 (s, 2H), 4.77 (s,
1H), 4.62e4.60 (m, 1H), 4.10e4.02 (m, 7H), 3.71 (s, 2H), 3.22e3.13
(m, 1H), 2.64e2.45 (m, 2H), 2.35e2.31 (m, 2H), 2.21e2.13 (m, 1H),
1.76 (s, 3H), 1.13e0.99 (m, 42H). 13C NMR (75 MHz, acetone-d6)
NMR (300 MHz, acetone-d6) d 8.17e8.16 (m, 4H), 7.45e7.27 (m,
20H), 7.05 (br s, 2H), 6.89 (br s, 2H), 6.72e6.49 (m, 9H), 6.49e6.42
(m, 2H), 5.87e5.85 (m,1H), 5.07e5.02 (m,13H), 4.94 (s, 2H), 4.84 (d,
1H), 4.19e4.10 (m, 3H), 3.99 (t, 1H), 3.78e3.63 (m, 2H), 3.18e3.09
(m, 1H), 2.99e2.90 (m, 1H), 2.54e2.47 (m, 1H), 2.40e2.34 (m, 1H),
d
164.4, 163.6, 161.0, 160.8, 152.8, 152.5, 151.3, 151.1, 145.7, 144.2,
1.11e1.03 (m, 28H). 13C NMR (75 MHz, acetone-d6)
d 161.1, 160.9,
143.8,140.7,138.1,136.4,134.8,134.5,133.5,133.1,129.3,129.2,129.1,
128.6, 128.4, 125.9, 111.0, 107.1, 105.6, 101.8, 101.3, 89.4, 88.2, 88.0,
88.0, 85.4, 85.1, 73.3, 73.0, 70.5, 70.3, 65.2, 63.8, 63.2, 62.3, 42.6,
40.9, 40.1, 17.9, 17.8, 17.7, 17.7, 17.7, 17.6, 12.8, 12.8, 12.7, 12.6, 12.5. 29Si
157.6, 157.5, 157.2, 157.1, 153.6, 153.1, 150.5, 149.7, 144.5, 141.3, 140.8,
140.6,138.2,129.3,128.7,128.5,121.5,120.9,107.2,105.7,101.9,101.5,
90.5, 88.4, 87.5, 85.2, 74.8, 73.5, 70.5, 70.3, 65.3, 63.9, 63.6, 41.6, 40.1,
17.9, 17.8, 17.7, 17.7, 12.9, 12.9, 12.7, 12.6. MALDI-TOF (m/z): [MþNa]þ
calcd for C81H94NaN10O13Si2: 1493.6, found 1494.5.
NMR (53.5 MHz, acetone-d6)
d
ꢀ7.07. MALDI-TOF (m/z): [MþNa]þ
calcd for C110H128NaN10O21Si3: 2031.8, found 2032.8.
Acknowledgements
4.4.2. Gi-BuCBzABzTD2. Following the procedure for preparing
A
BzTD2, 0.80 equiv (201 mg) of CBzABzTD2 was coupled with in-
We are grateful to the financial support from the National Basic
Research Program of China (973 program, No. 2007CB935900 &
2011CB935701), the National Natural Science Foundation of China
(No. 20725309 & 91027046) and NSFC-DFG joint project TRR61.
termediate G (0.92 equiv), and the detritylated residue was purified
by silica gel column chromatography using EtOAc/MeOH¼20:1 as
eluent to give Gi-BuCBzABzTD2 (130 mg, 52% yield for two steps) as
white foam. 1H NMR (300 MHz, acetone-d6)
d 12.06 (br s, 1H), 10.80
(br s, 1H), 10.19 (br s, 1H), 10.09 (br s, 1H), 8.65 (s, 1H), 8.48 (s, 1H),
8.23 (d, J¼7.5 Hz, 1H), 8.11e8.05 (m, 5H), 7.59e7.30 (m, 28H),
6.73e6.55 (m, 10H), 6.34e6.23 (m, 2H), 6.17e6.12 (m, 1H),
5.08e5.03 (m, 13H), 4.88 (s, 2H), 4.77e4.70 (m, 3H), 4.51 (s, 1H),
4.13e4.00 (m, 10H), 3.70 (s, 2H), 3.20e3.14 (m, 1H), 3.01e2.92 (m,
1H), 2.81e2.73 (m, 1H), 2.63e2.59 (m, 2H), 2.36e2.33 (m, 3H),
2.29e2.22 (m, 1H), 1.77 (s, 3H), 1.22e1.19 (m, 6H), 1.13e1.03 (m,
Supplementary data
1H NMR of T1D2 and T2D2 by precipitation and chromatography;
1H NMR chemical shifts of T2D2$A2D2 (i) in DMSO, (ii) titration with
DMSO, (iii) variable temperature studies, (iv) determination of as-
sociation constant Ka for T2D2$A2D2 and T2$A2; FT-MS spectrum of
T2D2$A2D2; and characterization data for new compounds. Sup-
plementary data associated with this article can be found in the
MOL files and InChIKeys of the most important compounds de-
scribed in this article.
56H). 13C NMR (75 MHz, acetone-d6)
d 180.9, 164.5, 163.9, 161.1,
160.9,156.0, 152.8,151.4,151.1,149.3,149.1,145.2,144.3,143.9,140.8,
138.6, 138.2, 136.5, 134.5, 133.6, 133.3, 129.4, 129.3, 129.2, 128.7,
128.5, 125.9, 121.9, 111.1, 107.2, 105.7, 101.9, 101.4, 89.5, 88.8, 88.6,
88.1, 85.4, 84.9, 74.1, 73.5, 73.1, 70.5, 70.3, 65.3, 63.8, 63.4, 62.8, 42.4,
41.4, 40.9, 40.1, 36.4, 19.5, 18.0, 17.9, 17.8, 12.9, 12.9, 12.8, 12.7, 12.6.
29Si NMR (53.5 MHz, acetone-d6)
d
ꢀ6.22, ꢀ6.83. MALDI-TOF (m/z):
References and notes
[MþNa]þ calcd for C130H159NaN15O26Si4: 2481.1, found 2481.1.
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4.4.3. GCATD2. Gi-BuCBzABzTD2 (10 mg) was added into 3 mL mix-
ture solvent of ethane-1,2-diamine/ethanol (1:1) and stirred at
55 ꢁC for 50 min. The solvent was removed to give GCATD2. MALDI-
TOF (m/z): [MþNa]þ calcd for C112H145NaN15O23Si4: 2203.0, found
2204.3.
4.4.4. ABz1D2. Following the procedure for preparing T1D2,
0.92 equiv (2.10 g, 3.04 mmol) of D2OH was coupled with in-
termediate A (0.92 equiv). After detritylation in 3% dichloroacetic
acid in CH2Cl2 (50 mL) for 5 min, crude product was purified by
silica gel column chromatography using CH2Cl2/EtOAc¼2:1 as el-
uent to give ABz1D2 (2.31 g, 63% yield for two steps) as white foam.
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1H NMR (300 MHz, acetone-d6)
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7.47e7.28 (m, 20H), 6.75e6.54 (m, 10H), 5.09e4.91 (m, 15H),
4.16e4.14 (m, 1H), 3.85e3.68 (m, 2H), 3.03e2.94 (m, 1H), 2.53e2.46
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(m, 1H), 1.13e1.12 (m, 14H). 13C NMR (75 MHz, acetone-d6)
d 166.0,
161.1,161.0,152.5,151.4,144.5,143.9,140.8,138.2,135.0,133.3,129.4,
129.3, 129.2, 128.9, 128.7, 128.5, 126.2, 107.2, 105.8, 102.1, 101.7, 90.2,
86.7, 74.3, 70.6, 70.5, 65.4, 63.3, 41.7, 18.0, 13.0, 12.9. MALDI-TOF (m/
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0.92 equiv (2.10 g) of ABz1D2 was coupled with intermediate A
(0.92 equiv). Detritylation in 3% dichloroacetic acid in CH2Cl2
(50 mL), gave crude ABz2D2, which was directly used for the next
step without further purification. ABz2D2 was added into 20 mL
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