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Catalysis Science & Technology
mixture was stirred at rt for 16 h and then the volatiles were solid was purified via flash column chromatography (SiO2 60,
removed under reduced pressure. The resulting yellowish CH2Cl2 : n-pentane = 2 : 5; (Sa,Sa,SC,SC)-L2: Rf = 0.61). Yield =
solid was purified via flash column chromatography (SiO2, 198 mg (69%).
CH2Cl2 : n-pentane
(Sa,Sa,SC,SC)-L2: Rf = 0.61). Yield: (Sa,SC,SC,RP)-L1 = 194 mg 7.93 (d, 1H, J = 9.1 Hz, Ar), 7.90 (d, 1H, J = 8.9 Hz, Ar), 7.89
(45%); (Sa,Sa,SC,SC)-L2 = 83 mg (12%). (d, 1H, J = 7.9 Hz, Ar), 7.86 (d, 1H, J = 8.3 Hz, Ar), 7.81 (d, 1H, J =
=
2 : 5; (Sa,SC,SC,RP)-L1: Rf
=
0.79,
1H-NMR (600 MHz, CDCl3): d = 7.99 (d, 1H, J = 8.0 Hz, Ar),
1H-NMR (600 MHz, CDCl3): d = 8.04 (d, 1H, J = 8.8 Hz, Ar), 9.0 Hz, Ar), 7.71 (d, 1H, J = 9.0 Hz, Ar), 7.69 (d, 1H, J = 8.3 Hz,
7.97 (d, 1H, J = 8.2 Hz, Ar), 7.90 (d, 1H, J = 7.9 Hz, Ar), 7.81 Ar), 7.49 (m, 1H, Ar), 7.44 (m, 1H, Ar), 7.38–7.29 (m, 7H, Ar),
(d, 1H, J = 8.8 Hz, Ar), 7.68 (d, 1H, J = 8.8 Hz, Ar), 7.54 (d, 1H, J = 7.27–7.23 (m, 5H, Ar), 7.22–7.17 (m, 2H, Ar), 7.10–7.05 (m, 7H,
8.8 Hz, Ar), 7.51 (m, 1H, Ar), 7.48–7.42 (m, 3H, Ar), 7.39–7.31 Ar), 7.03 (d, 1H, J = 8.5 Hz, Ar), 6.98 (t, 1H, J = 7.4 Hz, Ar), 6.92
(m, 8H, Ar), 7.28–7.22 (m, 4H, Ar), 6.85–6.76 (m, 3H, Ar), 6.22 (t, 2H, J = 7.9 Hz, Ar), 6.72 (t, 1H, J = 7.4 Hz, Ar), 6.67 (d, 2H, J =
(d, 2H, J = 7.9 Hz, Ar), 4.54 (m, 2H, CHCH3), 1.84 (d, 6H, J = 7.0 Hz, 7.7 Hz, Ar), 6.65–6.59 (m, 4H, Ar), 6.48 (d, 1H, J = 8.9 Hz, Ar),
CH3) ppm. 13C{1H}-NMR (150 MHz, CDCl3): d = 150.60 (Cq), 6.17 (d, 1H, J = 9.0 Hz, Ar), 5.61 (s, 1H, OH), 5.55 (s, 1H, OH),
148.20 (d, J = 26.2 Hz, Cq), 143.10 (d, J = 1.4 Hz, 2Cq), 141.84 4.31 (s br, 2H, CHCH3), 0.87 (d, 6H, J = 8.0 Hz, CH3) ppm.
(d, J = 5.4 Hz, Cq), 133.12 (d, J = 2.4 Hz, Cq), 132.83 (Cq), 131.83 13C{1H}-NMR (150 MHz, CDCl3): d = 150.59 (d, J = 6.3 Hz, Cq),
(Cq), 131.32 (Cq), 130.37 (CH), 129.88 (Cq), 129.59 (CH), 128.92 150.43 (d, J = 7.6 Hz, Cq), 143.07 (Cq), 142.91 (Cq), 142.63 (2Cq),
(2CH), 128.90 (2CH), 128.60 (d, J = 1.4 Hz, 2CH), 128.51 (CH), 139.83 (Cq), 139.61 (Cq), 134.95 (Cq), 134.82 (Cq), 134.24 (Cq),
128.11 (2CH), 128.05 (CH), 128.03 (4CH), 127.14 (2CH), 126.55 133.61 (Cq), 130.53 (Cq), 130.08 (Cq), 129.72 (Cq), 129.54 (Cq),
(CH), 126.21 (CH), 126.06 (CH), 125.84 (d, J = 5.5 Hz, Cq), 125.45 129.46 (CH), 129.39 (CH), 129.32 (2CH), 128.94 (2CH), 128.90
(CH), 124.59 (CH), 122.52 (d, J = 2.3 Hz, CH), 121.42 (CH), (CH), 128.75 (CH), 128.35 (4CH), 128.29 (CH), 128.14 (2CH),
121.07 (d, J = 12.7 Hz, 2CH), 54.21 (CHCH3), 54.14 (CHCH3), 127.95 (CH), 127.77 (4CH), 126.84 (CH), 126.81 (2CH), 126.44
21.85 (2CHCH3) ppm. 31P{1H}-NMR (243 MHz, CDCl3): d = (2CH), 126.43 (CH), 125.81 (2CH), 125.65 (CH), 125.42 (CH),
142.72. HRMS (ESI): m/z = calcd for C68H54N3O2P: 614.24815; 124.48 (2CH), 123.43 (CH), 123.17 (CH), 121.67 (CH), 121.60
found: 614.24627; [a]2D0 = ꢀ2581 (c = 0.1, CH2Cl2).
(d, J = 2.9 Hz, Cq), 121.02 (d, J = 2.6 Hz, Cq), 120.95 (CH), 120.56
(11bS)-5-Phenyl-N,N-bis((R)-1-phenylethyl)dinaphtho[2,1-d:10,20-f]- (d, J = 11.6 Hz, CH), 119.91 (d, J = 17.5 Hz, CH), 119.54 (2CH),
[1,3,2]oxazaphosphepin-4(5H)-amine (Sa,RC,RC,RP)-L1. The 119.32 (CH), 118.99 (Cq), 118.32 (2CH), 118.30 (Cq), 117.90
same procedure as above. (RC,RC)-1 was used instead of (CH), 51.81 (CHCH3), 51.74 (CHCH3), 20.67 (2CHCH3) ppm.
(SC,SC)-1. Purification via flash column chromatography (SiO2, 31P{1H}-NMR (243 MHz, CDCl3): d = 141.17. HRMS (ESI): m/z =
CH2Cl2 : n-pentane
(Sa,Sa,RC,RC)-L2: Rf = 0.64). Yield: (Sa,RC,RC,RP)-L1 = 151 mg 1731 (c = 0.1, CH2Cl2).
(35%); (Sa,Sa,RC,RC)-L2 = 90 mg (13%).
(10S,100S)-20,200-((bis((R)-1-Phenylethyl)amino)phosphinediyl)-
= 2 : 5; (Sa,RC,RC,RP)-L1: Rf = =
0.75, calcd for C68H54N3O2P: 975.39482; found: 975.39520; [a]D20
1H-NMR (600 MHz, CDCl3): d = 7.96–7.93 (m, 3H, Ar), 7.92 bis(phenylazanediyl)di-1,10-bibenzobenzen-2-ol, (Sa,Sa,RC,RC)-L2.
(d, 1H, J = 8.1 Hz, Ar), 7.62 (d, 1H, J = 8.8 Hz, Ar), 7.51–7.44 The same procedure as above. (RC,RC)-1 was used instead of
(m, 4H, Ar), 7.35–7.28 (m, 3H, Ar), 7.20–7.12 (m, 12H, Ar), 7.08 (SC,SC)-1. Purification via flash column chromatography (SiO2,
(d, 2H, J = 8.1 Hz, Ar), 6.94 (7, 1H, J = 7.3 Hz, Ar), 4.60 (m, 2H, CH2Cl2 : n-pentane = 2:1); yield: = 199 mg (70%).
CHCH3), 1.93 (d, 6H, J = 7.0 Hz, CH3) ppm. 13C{1H}-NMR
1H-NMR (600 MHz, CDCl3): d = 7.96 (d, 1H, J = 9.0 Hz, Ar),
(150 MHz, CDCl3): d = 149.89 (Cq), 148.44 (d, J = 26.0 Hz, Cq), 7.93–7.89 (m, 3H, Ar), 7.85 (d, 1H, J = 8.0 Hz, Ar), 7.80 (d, 1H, J =
142.73 (b, 2Cq), 141.62 (d, J = 4.2 Hz, Cq), 132.93 (d, J = 2.2 Hz, Cq), 8.2 Hz, Ar), 7.69 (d, 1H, J = 9.0 Hz, Ar), 7.64 (d, 1H, J = 9.0 Hz,
132.74 (Cq), 131.85 (Cq), 131.22 (d, J = 1.2 Hz, Cq), 130.32 (Cq), Ar), 7.62 (d, 1H, J = 8.9 Hz, Ar), 7.48 (m, 1H, Ar), 7.48–7.42
130.15 (CH), 129.36 (CH), 128.76 (d, J = 1.3 Hz, 2CH), 128.47 (m, 1H, Ar), 7.39–7.35 (m, 2H, Ar), 7.32–7.25 (m, 5H, Ar),
(CH), 128.24 (4CH), 128.05 (CH), 127.97 (CH), 127.76 (CH), 7.25–7.18 (m, 3H, Ar), 7.17–7.07 (m, 6H, Ar), 7.02–6.97
127.67 (4CH), 126.58 (2CH), 126.37 (CH), 126.08 (CH), 126.03 (m, 3H, Ar), 6.91–6.87 (m, 2H, Ar), 6.84–6.78 (m, 6H, Ar), 6.67
(CH), 125.77 (d, J = 5.5 Hz, Cq), 125.50 (CH), 124.45 (CH), 122.20 (d, 2H, J = 7.6 Hz, Ar), 6.64 (d, 1H, J = 8.9 Hz, Ar), 6.45 (d, 1H, J =
(d, J = 2.3 Hz, CH), 121.78 (CH), 121.18 (d, J = 13.2 Hz, 2CH), 7.6 Hz, Ar), 6.28 (d, 1H, J = 9.0 Hz, Ar), 5.39 (s, 1H, NH), 5.18
54.12 (CHCH3), 54.05 (CHCH3), 22.15 (2CHCH3) ppm. (s, 1H, NH), 4.33 (m, 2H, CHCH3), 0.95 (d, 6H, J = 7.2 Hz, CH3)
31P{1H}-NMR (243 MHz, CDCl3): d = 135.00. HRMS (ESI): ppm. 13C{1H}-NMR (150 MHz, CDCl3): d = 150.84 (d, J = 8.6 Hz,
m/z = calcd for C68H54N3O2P: 614.24815; found: 614.24792; Cq), 150.30 (d, J = 1.8 Hz, Cq), 142.98 (2Cq), 142.57 (Cq), 142.24
[a]2D0 = 5791 (c = 0.1, CH2Cl2).
(Cq), 140.86 (Cq), 139.78 (Cq), 134.35 (Cq), 134.18 (Cq), 133.47
(10S,100S)-20,200-((bis((S)-1-Phenylethyl)amino)phosphinediyl)- (Cq), 133.42 (Cq), 130.97 (Cq), 130.25 (CH), 129.97 (Cq), 129.47
bis(phenylazanediyl)di-1,10-bibenzobenzen-2-ol, (Sa,Sa,SC,SC)-L2. (Cq), 129.38 (CH), 129.28 (Cq), 129.05 (2CH), 129.01 (CH),
To a solution of (Sa)-N-Ph-NOBIN (2 eq., 211.9 mg, 0.584 mmol) 128.96 (2CH), 128.82 (CH), 128.41 (4CH), 128.40 (CH), 128.08
in CH2Cl2 (5 mL) at 0 1C was added NEt3 (20 eq., 0.81 mL, (CH), 127.99 (CH), 127.87 (5CH), 126.96 (CH), 126.85 (CH),
5.84 mmol) via a syringe and then dropwise a solution of 126.81 (2CH), 126.53 (CH), 126.28 (CH), 125.37 (CH), 125.35
(SC,SC)-1 (1 eq., 95.3 mg, 0.292 mmol) in CH2Cl2 (10 mL). The (CH), 125.10 (CH), 125.08 (CH), 124.96 (CH), 124.35 (CH),
reaction mixture was stirred at rt for 5 h and then the volatiles 123.14 (CH), 123.13 (CH), 122.83 (d,
J = 3.5 Hz, Cq),
were removed under reduced pressure. The resulting yellowish 122.74 (d, J = 5.7 Hz, CH), 121.84 (2CH), 120.32 (2CH), 120.27
c
592 Catal. Sci. Technol., 2013, 3, 589--594
This journal is The Royal Society of Chemistry 2013