LETTER
Novel Axial Chiral Sulfur-oxazoline Ligands with a Biphenyl Backbone
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(8) (S,aR)-1a: 1H NMR (400 MHz, CDCl3) d 7.46-7.05 (m, 6H),
4.10 (q, 1H, J 8.2, 9.8 Hz), 3.90-3.82 (m, 1H), 3.65 (t, 1H, J
8.4 Hz), 3.76 (s, 3H), 2.33 (s, 3H),1.58 (m, 1H), 0.78 (m, 6H)
(S,aS)-1a: 1H NMR (400 MHz, CDCl3) d 7.46-7.05 (m, 6H),
4.14-4.08 (m, 1H), 3.90-3.82 (m, 2H), 3.77 (s, 3H), 2.35 (s,
3H), 1.58 (m, 1H), 0.78 (m, 6H). [a]D11 = -64.6 (c = 0.50
CHCl3). MS(FAB) m/z 342 [M+1]+. IR (neat) 744, 1049,
1257, 1435, 1466, 1651, 2956 cm-1. (S,aR)-1b: 1H NMR (400
MHz, CDCl3) d 7.47-7.07 (m, 7H), 4.06 (q, 1H, J 8.0, 9.6 Hz),
3.89-3.74 (m, 2H), 3.75 (s, 3H), 2.31 (s, 3H), 0.73 (s, 9H).
(S,aS)-1b: 1H NMR (400 MHz, CDCl3) d 7.47-7.00 (m, 7H),
3.93-3.74 (m, 2H), 3.76 (s, 3H), 2.30 (s, 3H), 0.73 (s, 9H).
[a]D11 = -64.6 (c = 0.50 CHCl3). MS(FAB) m/z 356 [M+1]+.
IR (neat) 746, 1047, 1261, 1479, 1651, 2952 cm-1. (S,aR)-2a:
1H NMR (400 MHz, CDCl3) d 7.48-7.09 (m, 7H), 3.96-3.82
(m, 2H), 3.36-3.29 (m, 1H), 3.75 (s, 3H), 1.60 (m, 2H), 1.20-
1.15 (dd, 6H, J 1.6, 6.8 Hz), 0.83-0.77 (m, 6H). [a]D10 = -8.9
(c = 0.50 CHCl3). MS(FAB) m/z 370 [M+1]+. IR (neat) 771,
1051, 1259, 1464, 1651, 2958 cm-1. (S,aS)-2a: 1H NMR (400
MHz, CDCl3) d 7.48-7.03 (m, 7H), 4.08 (q, 1H, J 8.0, 9.2 Hz),
3.62 (t, 1H, J 8.0 Hz), 3.26 (q, 1H, J 8.0, 9.2 Hz), 3.74 (s, 3H),
1.60 (m, 2H), 1.17 (d, 3H, J 6.8 Hz), 1.16 (d, 3H, J 6.8 Hz),
0.81 (d, 3H, J 6.8 Hz), 0.78 (d, 3H, J 6.8 Hz). [a]D10 = -51.9 (c
= 0.50 CHCl3). MS(FAB) m/z 370 [M+1]+. IR (neat) 746,
1051, 1257, 1466, 1651, 2958 cm-1. (S,aR)-2b: 1H NMR (400
MHz, CDCl3) d 7.47 (dd, 1H, J 1.6, 8.0 Hz), 7.39 (t, 1H, J 8.0
Hz), 7.28-7.24 (m, 2H), 7.21-7.17 (m, 1H), 7.10-7.04 (m, 2H),
3.92-3.79 (m, 3H), 3.74 (s, 3H), 3.33 (m, 1H), 1.20 (d, 3H, J
6.8 Hz), 1.17 (d, 3H, J 6.8 Hz), 0.76 (s, 9H). [a]D10 = -23.3 (c
= 0.50 CHCl3). MS(FAB) m/z 384 [M+1]+. IR (neat) 744,
1049, 1259, 1466, 1641, 2956 cm-1. (S,aS)-2b: 1H NMR (400
MHz, CDCl3) d 7.50-7.38 (m, 3H), 7.29-7.25 (m, 1H), 7.23-
7.16 (m, 2H), 7.06 (d, 1H, J 8.0 Hz), 4.05 (t, 1H, J 9.1 Hz),
3.86 (t, 1H, J 9.1 Hz), 3.75 (m, 1H), 3.74 (s, 3H), 3.27 (m, 1H),
1.18 (d, 3H, J 3.0 Hz), 1.16 (d, 3H, J 3.0 Hz), 0.78 (s, 9H).
[a]D10 = -62.3 (c = 0.50 CHCl3). MS(FAB) m/z 384 [M+1]+.
IR (neat) 746, 1049, 1259, 1466, 1655, 2956 cm-1.
Acknowledgement
This work was supported by a JSPS Research Fellowships for
Young Scientists and Grant-in-Aid for Scientific Research from the
Ministry of Education, Science, Sports and Culture of the Japanese
Government.
References and Notes
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(9) The absolute configulation of ligands 1 were assigned by the
analysis of NOE. Namely, the NOE patterns of the complexes
of these ligands were similar to that of chiral bisoxazoline
ligands having a biphenyl backbone.11
(10) (S,aS)-3a: 1H NMR (400 MHz, CDCl3) d 7.90-7.09 (m, 8H),
4.16 (q, 1H, J 8.2, 9.4 Hz), 3.93-3.76 (m, 3H), 2.31 (s, 3H),
1.60 (m, 1H), 0.81-0.79 (m, 6H). (S,aR)-3a: 1H NMR (400
MHz, CDCl3) d 7.90-7.09 (m, 8H), 4.02 (q, 1H, J 7.8, 9.0 Hz),
3.93-3.76 (m, 2H), 2.34 (s, 3H), 1.60 (m, 1H), 0.85-0.79 (m,
6H). [a]D12 = -31.4 (c = 0.50 CHCl3). MS(FAB) m/z 312
[M+1]+. IR (neat) 750, 1651, 2956 cm-1. (S,aS)-3b: 1H NMR
(400 MHz, CDCl3) d 7.91-7.08 (m, 8H), 4.10 (q, 1H, J 12.0,
14.0 Hz), 3.99-3.83 (m, 2H), 3.30 (s, 3H), 0.77 (s, 9H). (S,aR)-
3b: 1H NMR (400 MHz, CDCl3) d 7.91-7.08 (m, 8H), 3.99-
3.83 (m, 3H), 2.35 (s, 3H), 0.77 (s, 9H). [a]D12 = -45.9 (c =
0.50 CHCl3). MS(FAB) m/z 326 [M+1]+. IR (neat) 748, 1651,
2954 cm-1.
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Article Identifier:
1437-2096,E;1999,0,08,1319,1321,ftx,en;Y08999ST.pdf
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Synlett 1999, No. 8, 1319–1321 ISSN 0936-5214 © Thieme Stuttgart · New York