826
T. Shibata et al. / Tetrahedron 64 (2008) 821e830
18.2, 25.9, 26.0, 40.2, 40.7, 59.3, 59.6, 59.6, 61.3, 61.4, 126.9,
128.0, 128.1, 129.3, 129.8, 135.5, 136.6, 138.8, 139.0, 139.7,
171.4, 171.8; HRMS (FAB) for MꢁH found m/z 1249.6686,
calcd for C70H105O12Si4: 1249.6683. [a]2D6 34.3 (c 1.04,
CHCl3).
4.2.10. 7,70-Bis(4-bromophenyl)-5,6,50,60-tetrakis(tert-butyl-
dimethylsilyloxymethyl)-2,20-ditosyl-4,40-biisoindolinyl
(3cb)
Pale yellow solid; mp 240 ꢀC (decomp.); IR (CH2Cl2)
1
1354, 1255, 1165, 1068, 837 cmꢁ1; H NMR d¼ꢁ0.29 (s,
6H), ꢁ0.27 (s, 6H), ꢁ0.15 (s, 6H), ꢁ0.11 (s, 6H), 0.71 (s,
18H), 0.82 (s, 18H), 2.41 (s, 6H), 4.16 (d, J¼14.0 Hz, 2H),
4.25e4.41 (m, 10H), 4.49 (d, J¼10.6 Hz, 2H), 4.55 (d, J¼
10.6 Hz, 2H), 7.07 (d, J¼8.2 Hz, 2H), 7.26e7.33 (m, 6H),
7.57 (d, J¼8.2 Hz, 2H), 7.63e7.65 (m, 6H); 13C NMR d¼
ꢁ6.2, ꢁ5.9, ꢁ5.7, ꢁ5.6, 18.0, 18.2, 21.5, 25.7, 25.8, 53.9,
54.4, 58.7, 59.1, 121.9, 127.3, 129.9, 130.4, 130.9, 131.7,
133.4, 133.9, 134.9, 135.1, 137.0, 137.6, 137.8, 143.7;
HRMS (FAB) for MþH found m/z 1429.4292, calcd for
C70H99N2O8 Si4S279Br2: 1429.4287. [a]D23 3.3 (c 1.28, CHCl3).
4.2.7. 7,70-Diphenyl-2,2,20,20-tetrakis(ethoxycarbonyl)-
5,6,50,60-tetrakis(hydroxymethyl)-2,3,20,30-tetrahydro-
1H,10H-4,40-biindenyl (4ab)
1
Colorless oil; IR (neat) 2927, 1731, 1248, 706 cmꢁ1; H
NMR d¼1.16e1.22 (m, 12H), 3.26 (d, J¼17.2 Hz, 2H), 3.53
(d, J¼17.2 Hz, 2H), 3.65 (br s, 2H), 4.12e4.13 (m, 12H),
4.23 (d, J¼14.0 Hz, 2H), 4.51 (d, J¼11.6 Hz, 2H), 4.63 (d,
J¼14.0 Hz, 2H), 4.71 (d, J¼11.6 Hz, 2H), 4.94 (br s, 2H),
7.27e7.30 (m, 2H), 7.41e7.49 (m, 8H); 13C NMR d¼40.3,
40.8, 59.5, 60.0, 60.4, 61.7, 61.8, 127.4, 128.4, 128.6, 129.2,
129.2, 134.6, 137.7, 138.7, 139.0, 139.2, 171.2, 171.5; HRMS
(FAB) for MþH found m/z 795.3350, calcd for C46H51O12:
795.3381. [a]2D6 ꢁ45.4 (c 0.34, CHCl3, 89% ee). The enantio-
meric excess was determined by HPLC analysis using a chiral
column (Daicel Chiralpak IA: 4ꢂ250 mm, 254 nm UV detec-
tor, rt, eluent: 15%, 2-propanol in hexane, flow rate: 1.0 mL/
min, retention time: 15 min for minor isomer and 17 min for
major isomer).
4.2.11. 7,70-Bis(4-bromophenyl)-2,20-ditosyl-5,6,50,60-
tetrakis(hydroxymethyl)-4,40-biisoindolinyl (4cb)
White solid; mp 182 ꢀC; IR (CH2Cl2) 3307, 1344, 1162,
1
669 cmꢁ1; H NMR d¼2.42 (s, 6H), 3.69 (br s, 2H), 4.00
(d, J¼12.4 Hz, 2H), 4.10e4.29 (m, 6H), 4.39e4.46 (m, 4H),
4.54 (d, J¼12.0 Hz, 2H), 4.68 (d, J¼12.0 Hz, 2H), 4.96 (br
s, 2H), 7.10e7.12 (m, 2H), 7.24e7.26 (m, 2H), 7.32 (m,
4H), 7.61e7.65 (m, 8H); 13C NMR d¼21.6, 54.0, 54.1, 58.9,
60.0, 122.5, 127.2, 128.3, 130.1, 130.2, 130.6, 132.0, 132.1,
132.4, 133.4, 134.6, 135.9, 136.1, 137.3, 138.7, 138.8,
144.2; HRMS (FAB) for MþH found m/z 973.0825, calcd
for C46H43N2O8S279Br2: 973.0828. [a]2D3 ꢁ47.5 (c 1.39,
CHCl3, 82% ee). The enantiomeric excess was determined
by HPLC analysis using a chiral column (Daicel Chiralpak
IB: 4ꢂ250 mm, 254 nm UV detector, rt, eluent: 40%, 2-prop-
anol in hexane, flow rate: 1.0 mL/min, retention time: 7 min
for minor isomer and 10 min for major isomer).
4.2.8. 5,6,50,60-Tetrakis(tert-butyldimethylsilyloxymethyl)-
7,70-diphenyl-2,20-ditosyl-4,40-biisoindolinyl (3bb)
Colorless oil; IR (neat) 1354, 1255, 1165, 1066, 837 cmꢁ1
;
1H NMR d¼ꢁ0.28 (s, 6H), ꢁ0.26 (s, 6H), ꢁ0.19 (s, 6H),
ꢁ0.15 (s, 6H), 0.72 (s, 18H), 0.81 (s, 18H), 2.41 (s, 6H), 4.18
(d, J¼13.2 Hz, 2H), 4.27e4.44 (m, 10H), 4.53 (d, J¼10.4 Hz,
2H), 4.57 (d, J¼10.4 Hz, 2H), 7.18 (s, 2H), 7.31 (d, J¼8.0 Hz,
4H), 7.36e7.48 (m, 8H), 7.64 (d, J¼8.0 Hz, 4H); 13C NMR
d¼ꢁ6.2, ꢁ5.9, ꢁ5.8, ꢁ5.6, 18.1, 18.2, 21.5, 25.8, 25.8,
54.1, 54.5, 58.8, 59.2, 127.3, 127.6, 128.5, 128.7, 129.2, 129.9,
133.2, 134.1, 134.7, 135.1, 137.6, 137.8, 138.2, 143.6; HRMS
(FAB) for MꢁH found m/z 1271.5886, calcd for C70H99N2O8-
Si4S2: 1271.5920. [a]2D7 17.8 (c 2.22, CHCl3).
4.2.12. 5,6,50,60-Tetrakis(tert-butyldimethylsilyloxymethyl)-
2,20-ditosyl-7,70-bis(4-methoxyphenyl)-4,40-biisoindolinyl
(3db)
Dark yellow solid; mp 234 ꢀC; IR (CH2Cl2) 1352, 1250,
1
1164, 1064, 836 cmꢁ1; H NMR d¼ꢁ0.30 (s, 6H), ꢁ0.27 (s,
4.2.9. 7,70-Diphenyl-2,20-ditosyl-5,6,50,60-tetrakis-
(hydroxymethyl)-4,40-biisoindolinyl (4bb)
6H), ꢁ0.15 (s, 6H), ꢁ0.11 (s, 6H), 0.71 (s, 18H), 0.82 (s,
18H), 2.40 (s, 6H), 3.90 (s, 6H), 4.17 (d, J¼12.4 Hz, 2H),
4.26e4.45 (m, 10H), 4.50e4.58 (m, 4H), 6.95 (d, J¼8.4 Hz,
2H), 7.01 (d, J¼8.0 Hz, 2H), 7.11 (d, J¼8.4 Hz, 2H), 7.26e
7.32 (m, 6H), 7.64 (d, J¼8.4 Hz, 4H); 13C NMR d¼ꢁ6.2,
ꢁ5.9, ꢁ5.7, ꢁ5.5, 18.1, 18.2, 21.5, 25.8, 25.8, 54.2, 54.5,
55.4, 58.9, 59.2, 113.6, 114.0, 127.3, 129.9, 130.4, 133.1,
134.1, 134.6, 135.5, 137.6, 137.8, 138.1, 143.6, 159.0;
HRMS (FAB) for MꢁH found m/z 1331.6147, calcd for
C72H103N2O10Si4S2: 1331.6131. [a]2D3 8.3 (c 0.78, CHCl3).
White solid; mp 225 ꢀC (decomp.); IR (CH2Cl2) 3336,
1
1348, 1163, 1016, 667 cmꢁ1; H NMR d¼2.42 (s, 6H), 3.53
(br s, 2H), 4.01e4.04 (m, 2H), 4.14 (d, J¼13.8 Hz, 2H), 4.21
(d, J¼13.8 Hz, 2H), 4.31 (d, J¼14.0 Hz, 2H), 4.45e4.49 (m,
4H), 4.55e4.58 (m, 2H), 4.70 (d, J¼11.2 Hz, 2H), 4.97 (br
s, 2H), 7.22 (d, J¼8.0 Hz, 2H), 7.32e7.37 (m, 6H), 7.43e7.51
(m, 6H), 7.62 (d, J¼8.0 Hz, 4H); 13C NMR d¼21.5, 54.2,
54.2, 57.0, 60.0, 127.2, 128.1, 128.5, 128.9, 130.0, 132.2,
133.5, 134.4, 136.0, 137.3, 138.5, 138.7, 138.8, 144.1;
HRMS (FAB) for MþH found m/z 817.2609, calcd for
C46H45N2O8S2: 817.2617. [a]2D4 ꢁ37.1 (c 1.37, CHCl3, 86%
ee). The enantiomeric excess was determined by HPLC anal-
ysis using a chiral column (Daicel Chiralpak IB: 4ꢂ250 mm,
254 nm UV detector, rt, eluent: 40%, 2-propanol in hexane,
flow rate: 1.0 mL/min, retention time: 8 min for minor isomer
and 11 min for major isomer).
4.2.13. 2,20-Ditosyl-5,6,50,60-tetrakis(hydroxymethyl)-7,70-
bis(4-methoxyphenyl)-4,40-biisoindolinyl (4db)
White solid; mp 174 ꢀC; IR (CH2Cl2) 3311, 1346, 1248,
1
1161, 1016, 669 cmꢁ1; H NMR d¼2.42 (s, 6H), 3.60 (br s,
2H), 3.89 (s, 6H), 4.00 (d, J¼12.5 Hz, 2H), 4.12 (d, J¼
14.2 Hz, 2H), 4.20 (d, J¼14.2 Hz, 2H), 4.32 (d, J¼14.0 Hz,
2H), 4.47e4.55 (m, 6H), 4.68 (d, J¼11.5 Hz, 2H), 5.05 (br