Ru(II)-Catalyzed Hydrogenation of Aromatic Ketones in Water with Soluble Chiral Monosulfonamide Ligands 511
of 1-methylimidazole were removed under reduced
Anal. Calcd for C22H27F6N5O7S: C, 42.65; H, 4.39; N,
11.30; Found: C, 42.23; H, 4.17; N, 11.02.
pressure, and the residue was dried in vacuo to give
6a as a pale yellow solid (214 mg, 81.2%). m.p. 159–
161◦C. [α]D = +50 (c = 0.3, C2H5OH). IR (KBr), ν:
3550, 3478, 3423, 3105, 2936, 1689, 1597, 1544, 1318,
Preparation of (R,R)-7b
1
1161 cm−1. H NMR (DMSO-d6, 400 MHz): δ 0.98–
Compound 7b was prepared using the same proce-
dure as 7a, yield 99%. m.p. 132–134◦C. [α]D = +69.8
(c = 0.32, CH3OH). IR (KBr), ν: 3418, 3068, 2947,
1.76 (m, 8H), 1.38 (s, 9H), 2.86 (br s, 1H), 3.14 (br
s, 1H), 3.93 (s, 3H), 5.28 (s, 2H), 6.37 (d, J = 8 Hz,
1H), 7.44 (d, J = 8 Hz, 1H), 7.74 (d, J = 7.2 Hz, 2H),
7.76 (d, J = 6.8 Hz, 2H), 9.12 (s, 1H), 11.13 (s, 1H).
Anal. Calcd for C23H34ClN5O5S: C, 52.31; H, 6.49; N,
13.26; Found: C, 52.01; H, 6.71; N, 13.01.
1
1680, 1598, 1549, 1497, 1321, 1263, 1200 cm−1. H
NMR (DMSO-d6, 400 MHz): δ 0.96–1.97 (m, 8 H),
2.76 (br s, 1H), 2.96 (br s, 1H), 5.73 (s, 2H), 7.82 (s,
4H), 8.24 (s, 2H), 8.71 (t, J = 7.2 Hz, 1H), 9.07 (s,
2H), 11.34 (s, 1H). Anal. Calcd for C23H26F6N4O7S: C,
44.81; H, 4.25; N, 9.09; Found: C, 44.31; H, 4.47; N,
8.62.
Preparation of (R,R)-6b
Compound 6b was prepared using the same proce-
dure as 6a, yield 77.2% (two steps). m.p. 215–218◦C.
[α]D = +69.3 (c = 0.3, C2H5OH). IR (KBr), ν: 3338,
2937, 1685, 1598, 1550, 1524, 1319, 1259, 1157, 1090
cm−1. 1H NMR (DMSO-d6, 400 MHz): δ 0.97–1.75 (m,
8 H), 1.38 (s, 9 H), 2.83–2.85 (m, 1H), 3.12–3.14 (m,
1H), 5.75 (s, 2H), 6.37 (d, J = 8 Hz, 1H), 7.45 (d,
J = 8 Hz, 1H), 7.77 (d, J = 8.8 Hz, 2H), 7.80 (d, J =
9.2 Hz, 2H), 8.24 (t, J = 6.8 Hz, 2H), 8.71 (t, J = 7.6
Hz, 1H), 9.08 (d, J = 5.6 Hz, 2H), 11.51 (s, 1H). Anal.
Calcd for C24H33ClN4O5S: C, 54.90; H, 6.33; N, 10.67;
Found: C, 54.57; H, 6.61; N, 10.34.
Preparation of (R,R)-7c
Compound 7c was prepared using the same proce-
dure as 7a, yield 99%. m.p. 84–86◦C. [α]D = +47.7
(c = 0.35, CH3OH). IR (KBr), ν: 3419, 2947, 1680,
1599, 1548, 1467, 1323, 1201 cm−1. 1H NMR (DMSO-
d6, 400 MHz): δ 0.85–1.96 (m, 8 H), 1.29 (s, 9 H), 2.76
(br s, 1H), 2.96 (br s, 1H), 3.55 (d, J = 6.8 Hz, 6H),
4.29 (s, 2H), 7.84 (d, J = 9.2 Hz, 4H), 11.32 (s, 1H).
Anal. Calcd for C24H36F6N4O7S: C, 45.14; H, 5.68; N,
8.77; Found: C, 44.91; H, 5.92; N, 8.33.
Preparation of (R,R)-6c
(R,R)-N-(3-Nitrophenylsulfonyl)-1,2-
diaminocyclohexane (2b)
Compound 6c was prepared using the same proce-
dure as 6a, yield 88.4% (two steps). m.p. 152–155◦C.
[α]D = +45.3 (c = 0.3, C2H5OH). IR (KBr), ν: 3411,
2933, 1697, 1598, 1547, 1318, 1255, 1159, 1090 cm−1.
1H NMR (DMSO-d6, 400 MHz): δ 0.97–1.74 (m, 8 H),
1.29 (s, 9 H), 1.37 (s, 9 H), 2.86–2.88 (m, 1H), 3.06–
3.12 (m, 1H), 3.53 (d, J = 6 Hz, 6H), 4.37 (s, 2H), 6.37
(d, J = 5.6 Hz, 1H), 7.48 (d, J = 7.6 Hz, 1H), 7.78
(d, J = 8.4 Hz, 2H), 7.84 (d, J = 7.6 Hz, 2H), 11.51
(s, 1H). Anal. Calcd for C25H43ClN4O5S: C, 54.88; H,
7.92; N, 10.24; Found: C, 54.51; H, 8.21; N, 10.03.
Compound 2b was prepared using the same proce-
dure as 2a, using 3-nitrophenylsulfonyl chloride in-
stead of 4-nitrophenylsulfonyl chloride, yield 84.5%.
m.p. 110–112◦C. [α]D = −34.0 (c = 0.5, CHCl3). IR
(KBr), ν: 3570, 3375, 3302, 1670, 1534, 1352, 1324,
1164, 1099, 1082 cm−1. 1H NMR (CDCl3, 400 MHz): δ
1.17–1.68 (m, 8H), 1.91–1.97 (m, 3H), 2.38–2.41 (m,
1H), 2.68–2.73 (m, 1H), 7.74 (t, J = 8 Hz, 1H), 8.23
(d, J = 8 Hz, 1H), 8.41–8.42 (m, 1H), 8.77 (s, 1H).
Anal. Calcd for C12H17N3O4S: C, 48.15; H, 5.72; N,
14.04; Found: C, 48.27; H, 5.61; N, 14.19.
Preparation of (R,R)-7a
(R,R)-N-Boc-Nꢁ-(3-nitrophenylsulfonyl)-1,2-
Trifluoroacetic acid (4.5 mL) was added to (R,R)-6a
(264 mg, 0.5 mmol) at 0◦C under argon. After stirring
for 4 h at 0◦C, toluene (12 mL) was added to the
mixture and the volatile was removed under reduced
pressure to give 7a as a pale yellow solid (99%). m.p.
88–90◦C. [α]D = +35.8 (c = 0.5, CH3OH). IR (KBr), ν:
3418, 3114, 2947, 1680, 1598, 1549, 1323, 1201 cm−1.
1H NMR (DMSO-d6, 400 MHz): δ 0.95–1.96 (m, 8 H),
2.67–2.82 (m, 1H), 2.94 (br s, 1H), 3.87 (s, 3H), 5.27
(s, 2H), 6.62 (d, J = 8 Hz, 1H), 7.45 (d, J = 8 Hz,
1H), 7.74–7.81 (m, 4H), 9.05 (s, 1H), 11.09 (s, 1H).
diaminocyclohexane (3b)
Compound 3b was prepared using the same pro-
cedure as 3a, yield 87.3%. m.p. 115–118◦C. [α]D
=
+11.9 (c = 0.42, C2H5OH). IR (KBr), ν: 3364, 3221,
1690, 1611, 1533, 1352, 1324, 1167, 1080 cm−1. H
1
NMR (CDCl3, 400 MHz): δ 1.17–2.05 (m, 8H), 1.43 (s,
9H), 3.02–3.04 (m, 1H), 3.37–3.39 (m, 1H), 4.45 (d,
J = 7.2 Hz, 1H), 6.18 (d, J = 4.8 Hz, 1H), 7.72 (t, J =
8 Hz, 1 H), 8.20 (d, J = 8 Hz, 1H), 8.41–8.43 (m, 1H),
8.72 (t, J = 2 Hz, 1H). Anal. Calcd for C17H25N3O6S:
Heteroatom Chemistry DOI 10.1002/hc