Job/Unit: O20556
/KAP1
Date: 19-06-12 15:06:46
Pages: 9
C. S. Marques, A. J. Burke
FULL PAPER
3 H, CH3), 5.04–5.05 (d, 1 H, CH), 5.52–5.54 (d, 1 H, NH), 7.03–
7.07 (m, 4 H, Ar), 7.15–7.19 (m, 4 H, Ar), 7.21–7.23 (m, 3 H, Ar),
7.54–7.56 (d, 2 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ =
21.64 (CH3), 60.83 (CH), 126.62, 127.34, 127.43, 127.89, 128.07,
128.30, 128.79, 128.90, 128.92, 129.59, 129.76, 130.01, 132.51,
133.64, 137.28, 139.07, 140.19, 143.63 ppm. MS (ESI-TOF): m/z =
394.07 [M + 1]+. HPLC [Chiralcel OD-H column, hexane/2-propa-
nol (93:7), flow rate = 1.0 mL/min, wavelength detector at 230 nm]:
tR = 18.0 (S), 24.0 (R) min.
umn, hexane/2-propanol (80:20), flow rate = 0.5 mL/min, wave-
length detector at 230 nm]: tR = 12.3 (R), 15.3 (S) min.
N-[(4-Bromophenyl)(phenyl)methyl]-4-methylbenzenesulfonamide:[7,17,48]
1
White solid (12% yield). H NMR (400 MHz, CDCl3): δ = 2.40 (s,
3 H, CH3), 4.96–4.98 (d, 1 H, CH), 5.51–5.52 (d, 1 H, NH), 6.99–
7.05 (m, 4 H, Ar), 7.15–7.17 (d, 2 H, Ar), 7.21–7.23 (m, 3 H, Ar),
7.31–7.35 (m, 2 H, Ar), 7.54–7.56 (m, 2 H, Ar) ppm. 13C NMR
(100 MHz, CDCl3): δ = 21.74 (CH3), 60.99 (CH), 121.79, 126.64,
127.35, 127.43, 128.11, 128.92, 129.27, 129.60, 129.89, 131.74,
136.84, 137.09, 137.38, 138.24, 139.56, 140.10, 143.52, 143.86 ppm.
MS (ESI-TOF): m/z = 440.02 [M + 1]+. HPLC [Chiralcel OD-H
column, hexane/2-propanol (80:20), flow rate = 0.7 mL/min, wave-
length detector at 230 nm]: tR = 11.6 (S), 14.2 (R) min.
N-[Cyclohexyl(phenyl)methyl]-4-methylbenzenesulfonamide:[7,17,48]
Light yellow oil (17% yield). 1H NMR (400 MHz, CDCl3): δ =
0.85–1.10 (m, 3 H, CH2), 1.22–1.28 (m, 4 H, CH2), 1.33–1.59 (m,
4 H, CH2), 2.41 (s, 3 H, CH3), 3.30–3.32 (d, 1 H, CH), 4.85–4.87
(d, 1 H, NH), 7.29–7.36 (m, 5 H, Ar), 7.67–7.69 (d, 2 H, Ar), 7.79–
7.83 (d, 2 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.65
(CH3), 22.37 (CH2), 22.88 (CH2), 25.81 (CH2), 26.55 (CH2), 28.89
(CH2), 38.53 (CH), 66.33 (CH), 126.56, 126.63, 127.02, 127.13,
128.22, 129.57, 129.88, 130.06, 130.71, 139.05, 143.30, 145.13 ppm.
MS (ESI-TOF): m/z = 266.13 [M + 1 – Ph]+. HPLC [Chiralcel
OD-H column, hexane/2-propanol (80:20), flow rate = 0.5 mL/min,
wavelength detector at 230 nm]: tR = 10.9 (S), 14.0 (R) min.
N-[(2-Chlorophenyl)(phenyl)methyl]-4-methylbenzenesulfonamide:[7,17,48]
1
White solid (63% yield). H NMR (400 MHz, CDCl3): δ = 2.38 (s,
3 H, CH3), 5.31–5.33 (d, 1 H, CH), 5.90–5.92 (d, 1 H, NH), 7.05–
7.08 (m, 2 H, Ar), 7.14–7.16 (m, 4 H, Ar), 7.22–7.24 (m, 4 H, Ar),
7.33–7.35 (m, 1 H, Ar), 7.60–7.62 (d, 2 H, Ar) ppm. 13C NMR
(100 MHz, CDCl3): δ = 21.64 (CH3), 58.77 (CH), 127.07, 127.35,
127.39, 127.98, 128.78, 128.79, 128.79, 128.97, 129.48, 129.55,
129.56, 129.57, 130.03, 132.93, 137.05, 137.61, 139.40, 143.52 ppm.
MS (ESI-TOF): m/z = 394.07 [M + 1]+. HPLC [Chiralcel AD-H
column, hexane/2-propanol (90:10), flow rate = 0.7 mL/min, wave-
length detector at 230 nm]: tR = 27.9 (S), 31.8 (R) min.
4-Methyl-N-[naphthalen-2-yl(phenyl)methyl]benzenesulfonamide:[7,17,48]
Yellow solid (12% yield). 1H NMR (400 MHz, CDCl3): δ = 2.42
(s, 3 H, CH3), 5.41–5.43 (d, 1 H, CH), 5.72–5.74 (d, 1 H, NH),
7.02–7.04 (d, 1 H, Ar), 7.14–7.23 (m, 4 H, Ar), 7.28–7.30 (d, 2 H,
Ar), 7.43–7.45 (m, 2 H, Ar), 7.50 (s, 1 H, Ar), 7.53–7.55 (d, 2 H,
Ar), 7.63–7.68 (m, 2 H, Ar), 7.79–7.81 (d, 2 H, Ar) ppm. 13C NMR
(100 MHz, CDCl3): δ = 21.49 (CH3), 61.59 (CH), 122.89, 125.28,
126.37, 126.50, 126.56, 127.31, 127.60, 127.65, 127.81, 128.09,
128.61, 128.73, 129.42, 129.84, 132.75, 133.11, 137.39, 137.63,
139.20, 140.52, 143.37, 143.71 ppm. MS (ESI-TOF): m/z = 410.12
[M + 1]+. HPLC [Chiralcel OD-H column, hexane/2-propanol
(80:20), flow rate = 0.5 mL/min, wavelength detector at 230 nm]:
tR = 20.2 (R), 22.1 (S) min.
N-[(2-Chlorophenyl)(4-chlorophenyl)methyl]-4-methylbenzenesulfon-
amide:[7,17,48] White solid (12 % yield). 1H NMR (400 MHz,
CDCl3): δ = 2.37 (s, 3 H, CH3), 5.41–5.42 (d, 1 H, CH), 5.87–5.89
(d, 1 H, NH), 7.01–7.04 (d, 2 H, Ar), 7.14–7.25 (m, 8 H, Ar), 7.58–
7.60 (d, 2 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.70
(CH3), 58.23 (CH), 127.30, 128.78, 128.89, 129.24, 129.39, 129.59,
129.85, 130.02, 130.18, 130.34, 130.62, 132.86, 133.85, 135.77,
136.96, 137.16, 137.95, 143.65 ppm. MS (ESI-TOF): m/z = 428.03
[M + 1]+. HPLC [Chiralcel OD-H column, hexane/2-propanol
(70:30), flow rate = 0.7 mL/min, wavelength detector at 230 nm]:
tR = 8.2 (S), 11.7 (R) min.
N-[(4-Chlorophenyl)(phenyl)methyl]methanesulfonamide: White so-
lid (10% yield). 1H NMR (400 MHz, CDCl3): δ = 2.70 (s, 3 H,
CH3), 5.17–5.18 (m, 1 H, CH), 5.73–5.75 (m, 1 H, NH), 7.28–7.40
(m, 9 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 42.18 (CH3),
60.79 (CH), 127.45, 127.48, 128.45, 128.93, 129.19, 129.24, 129.25,
129.91, 132.53, 134.06, 139.33, 140.29 ppm. MS (ESI-TOF): m/z =
318.04 [M + 1]+. HPLC [Chiralcel OD-H column, hexane/2-prop-
anol (80:20), flow rate = 0.5 mL/min, wavelength detector at
230 nm]: tR = 15.2, 18.1 min.
4-Methyl-N-[(4-nitrophenyl)(phenyl)methyl]benzenesulfonamide:[7,17,48]
1
Light orange solid (Ͻ10% yield). H NMR (400 MHz, CDCl3): δ
= 2.40 (s, 3 H, CH3), 5.25–5.27 (d, 1 H, CH), 5.61–5.62 (d, 1 H,
NH), 6.98–7.00 (d, 2 H, Ar), 7.17–7.19 (d, 2 H, Ar), 7.35–7.39 (m,
4 H, Ar), 7.57–7.59 (m, 3 H, Ar), 8.07–8.09 (d, 2 H, Ar) ppm. 13C
NMR (100 MHz, CDCl3): δ = 21.70 (CH3), 61.07 (CH), 123.80,
124.45, 126.85, 127.20, 127.34, 127.44, 128.38, 128.56, 128.60,
129.26, 129.74, 130.64, 136.96, 139.40, 142.85, 144.04, 147.35,
147.80 ppm. MS (ESI-TOF): m/z = 405.09 [M + 1]+. HPLC [Chi-
ralcel AD-H column, hexane/2-propanol (90:10), flow rate =
0.7 mL/min, wavelength detector at 230 nm]: tR = 19.9 (S), 25.5 (R)
min.
4-Methyl-N-(1-phenylbutyl)benzenesulfonamide:[7,17,48] Colorless oil
1
(13% yield). H NMR (400 MHz, CDCl3): δ = 0.84–0.98 (m, 3 H,
CH3), 1.60–1.67 (m, 2 H, CH2), 2.28–2.32 (m, 2 H, CH2), 2.24 (s,
3 H, CH3), 4.07–4.11 (d, 1 H, CH), 4.21–4.25 (d, 1 H, NH), 7.31–
7.83 (m, 9 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 18.61
(CH3), 19.89 (CH2), 29.75 (CH3), 44.89 (CH2), 64.63 (CH), 126.15,
126.64, 127.20, 127.45, 127.49, 127.90, 128.34, 128.56, 129.01,
129.80, 129.85, 130.13 ppm. MS (ESI-TOF): m/z = 302.13 [M]+.
HPLC [Chiralcel OD-H column, hexane/2-propanol (80:20), flow
rate = 0.5 mL/min, wavelength detector at 230 nm]: tR = 15.0 (S),
16.3 (R) min.
Synthesis of the Chiral NHC Precursor 13
[(2S,3S,5S,6S)-5,6-Dimethoxy-5,6-dimethyl-1,4-dioxane-2,3-diyl]di-
methanamine (11):[35,36] To a round-bottomed flask containing di-
azide 10 (5 mmol), dry EtOH (50 mL), and Pd/C (10 mol-%) was
attached a rubber balloon filled with H2, and the mixture was
stirred 24 h. The mixture was then filtered through a sintered glass
filter, and the filtrate was concentrated under vacuum. The diamine
product (81 % yield) was obtained as a colorless oil. 1H NMR
(400 MHz, CDCl3): δ = 1.32 (s, 6 H, CH3), 1.83 (br. s, 4 H, NH2),
2.76 (d, 4 H, CH2), 3.28 (s, 3 H, OCH3), 3.59 (m, 2 H, CHO) ppm.
4-Methyl-N-[phenyl(o-tolyl)methyl]benzenesulfonamide:[7,17,48] Yel-
1
low solid (Ͻ10% yield). H NMR (400 MHz, CDCl3): δ = 2.17 (s,
3 H, CH3), 2.43 (s, 3 H, CH3), 5.30 (s, 1 H, CH), 6.02 (s, 1 H, NH),
7.06–7.23 (m, 5 H, Ar), 7.28–7.38 (m, 4 H, Ar), 7.51–7.56 (m, 2 H,
Ar), 7.80–7.82 (m, 2 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ
= 21.62 (CH3), 22.84 (CH3), 58.41 (CH), 125.80, 126.28, 126.30,
126.39, 126.63, 127.20, 127.26, 127.69, 127.74, 127.77, 128.64, N,NЈ-[(2R,3R,5S,6S)-5,6-Dimethoxy-5,6-dimethyl-1,4-dioxane-2,3-
128.70, 128.85, 129.47, 129.89, 130.70, 139.16, 143.81 ppm. MS diyl]bis(methylene)bis(1-phenylmethanamine) (12):[36] Diamine 11
(ESI-TOF): m/z = 374.13 [M + 1]+. HPLC [Chiralcel OD-H col-
(0.4 mmol) was added to a round-bottomed flask containing dry
6
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