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cals were purchased from Sigma–Aldrich, ABCR, TCI, or AlfaAesar 30 min at 0 °C and overnight at room temperature. The solution
and used as received.
was cooled to 0 °C, and a solution of 1-((R)-phenyl{[(R)-1-
phenylethyl]amino}methyl)naphthalen-2-ol (1.386 g, 3.92 mmol,
0.98 equiv.) and triethylamine (1.68 mL, 12.0 mmol, 3.0 equiv.) in
CH2Cl2 (10 mL) was added dropwise within 30 min. The mixture
was stirred for 30 min at 0 °C and 16 h at room temperature. Tolu-
ene (2 mL) was added, and all volatiles were removed at high vac-
uum. The residue was redissolved in toluene (12 mL) and the sus-
pension filtered through a PTFE membrane and basic alumina con-
secutively. After elution with THF (10 mL) all volatiles were removed
under reduced pressure to give a colorless solid. The residue was
recrystallized from toluene/ethanol. The precipitate was collected,
washed with small amounts of ethanol, and dried to yield the prod-
Synthetic Procedures
(1R,3R)-3-[2-(Diphenylphosphanyl)phenoxy]-1-phenyl-2-[(R)-1-
phenylethyl]-2,3-dihydro-1H-naphtho[1,2-e][1,3,2]oxazaphos-
phinine [(RC,RC,RP)-L10]: Method A in Scheme 1. 1-((R)-Phenyl{[(R)-
1-phenylethyl]amino}methyl)naphthalen-2-ol (706.9 mg, 2.0 mmol,
1.0 equiv.) was dissolved in THF (10 mL) and the solution cooled to
–78 °C. Afterwards n-butyllithium (1.6
M in hexanes, 2.53 mL,
4.04 mmol, 2.02 equiv.) was added dropwise within 15 min, and the
mixture was stirred for 1 h at –78 °C and 1 h at room temperature.
The solution was cooled again to –78 °C, and a solution of phos-
phorus trichloride (175 μL, 2.0 mmol, 1.0 equiv.) in THF (6 mL) was
added dropwise within 15 min. The mixture was stirred for 1 h at
–78 °C and another 1.5 h at room temperature. In another Schlenk
flask, 2-(diphenylphosphanyl)phenol (545.4 mg, 1.96 mmol,
0.98 equiv.) was dissolved in THF (10 mL), and TMEDA (300 μL,
2.0 mmol, 1.0 equiv.) was added. The solution was cooled to –78 °C
1
uct as a colorless solid. Yield: 683.4 mg (1.04 mmol, 26 %). H NMR
3
(400 MHz, CDCl3): δ = 1.47 (d, JH,H = 6.8 Hz, 3 H, CH3), 4.33 (dq,
3
3JH,H = 6.8, JH,P = 18.5 Hz, 1 H, CH), 5.58 (s, 1 H, CH), 6.50 (m, 1 H,
3
Ar), 6.80 (m, 5 H, Ar), 7.02–7.42 (m, 21 H, Ar), 7.55 (d, JH,H = 8.7 Hz,
1 H, Ar), 7.65 (m, 2 H, Ar) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ =
18.9 (dd, JC,P = 6.4, JC,P = 4.7 Hz, CH3), 55.0 (d, JC,P = 27.7 Hz, CH),
56.6 (d, JC,P = 5.4 Hz, CH), 117.7 (d, JC,P = 14.4 Hz, CH, Ar), 120.4
(CH, Ar), 121.6 (d, JC,P = 8.1 Hz, Cq, Ar), 122.5 (CH, Ar), 122.8 (CH,
Ar), 124.0 (CH, Ar), 126.1 (CH, Ar), 127.1 (CH, Ar), 127.2 (CH, Ar),
127.66 (CH, Ar), 127.73 (CH, Ar), 127.93 (CH, Ar), 128.04 (2 × CH, Ar),
128.22 (2 × CH, Ar), 128.25 (CH, Ar), 128.27 (2 × CH, Ar), 128.31 (CH,
Ar), 128.48 (CH, Ar), 128.59 (3 × CH, Ar), 128.60 (Cq, Ar), 129.2 (CH,
Ar), 129.9 (CH, Ar), 130.5 (Cq, Ar), 130.8 (Cq, Ar), 132.9 (CH, Ar), 133.1
and n-butyllithium (1.6
M in hexanes, 1.25 mL, 2.0 mmol, 1.0 equiv.)
was added dropwise within 15 min. The mixture was stirred for 1 h
at –78 °C and 1 h at 0 °C. The solution was cooled again to –78 °C,
and the solution of the phosphoramidochloridite (RC,RC,SP)-2 was
added dropwise within 15 min. The mixture was stirred for 2 h at
–78 °C and then allowed to reach room temperature overnight.
All volatiles were removed at high vacuum, and the residue was
redissolved in THF (10 mL) and filtered through basic alumina. After
elution with THF (10 mL), all volatiles were removed under reduced
pressure to give a colorless solid. The residue was recrystallized
from toluene/ethanol. The precipitate was collected, washed with
small amounts of ethanol, and dried to yield the product as a color-
less solid. Yield: 508.0 mg (0.77 mmol, 39 %). 1H NMR (400 MHz,
(CH, Ar), 133.4 (CH, Ar), 134.1 (CH, Ar), 134.3 (CH, Ar), 136.0 (d, JC,P
11.5 Hz, Cq, Ar), 137.0 (d, JC,P = 12.1 Hz, Cq, Ar), 141.1 (d, JC,P
=
=
5.2 Hz, Cq, Ar), 143.5 (d, JC,P = 2.2 Hz, Cq, Ar), 144.2 (d, JC,P = 2.8 Hz,
Cq, Ar), 155.7 (dd, JC,P = 17.3, JC,P = 4.8 Hz, Cq, Ar) ppm. 31P{1H} NMR
(162 MHz, CDCl3): δ = –15.5 (d, JP, P = 6.1 Hz), 112.1 (d, JP, P = 6.1 Hz)
ppm. EI-MS: m/z (%) = 555.2 (34), 554.1 (100), 540.1 (14), 278.0 (36),
+
3
3
276.0 (18), 199.0 (10), 105.1 (34). HRMS (ESI): calcd. for C43H36NO2P2
CDCl3): δ = 1.58 (d, JH,H = 6.9 Hz, 3 H, CH3), 4.74 (dq, JH,H = 6.8,
[M + H]+ 660.22158; found 660.22218. [α]2D5 = –240.4 (c = 0.5,
3JH,P = 13.4 Hz, 1 H, CH), 5.61 (d, JH,P = 6.4 Hz, 1 H, CH), 6.60 (ddd,
3
CH2Cl2).
J = 7.4, J = 3.7, J = 1.4 Hz, 1 H, Ar), 6.73 (dd, J = 7.9, J = 4.4 Hz, 1
H, Ar), 6.82–6.94 (m, 6 H, Ar), 7.05–7.27 (m, 20 H, Ar), 7.59 (m, 2 H,
Ar) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 20.8 (d, JC,P = 9.2 Hz,
CH3), 54.7 (d, JC,P = 4.6 Hz, CH), 58.1 (d, JC,P = 40.9 Hz, CH), 120.2
(dd, JC,P = 1.3, JC,P = 11.7 Hz, CH, Ar), 120.4 (d, JC,P = 6.4 Hz, Cq, Ar),
120.6 (d, JC,P = 3.4 Hz, CH, Ar), 121.9 (CH, Ar), 123.57 (CH, Ar), 123.61
(CH, Ar), 126.2 (CH, Ar), 126.6 (CH, Ar), 127.0 (CH, Ar), 127.30 (CH,
Ar), 127.32 (CH, Ar), 127.8 (2 × CH, Ar), 128.0 (2 × CH, Ar), 128.21
(CH, Ar), 128.26 (CH, Ar), 128.33 (2 × CH, Ar), 128.39 (CH, Ar), 128.41
(CH, Ar), 128.45 (CH, Ar), 128.8 (3 × CH, Ar), 129.0 (Cq, Ar), 129.6 (Cq,
Ar), 129.9 (CH, Ar), 130.8 (Cq, Ar), 133.82 (CH, Ar), 133.86 (CH, Ar),
(1S,3S)-3-[2-(Diphenylphosphanyl)phenoxy]-1-phenyl-2-[(R)-1-
phenylethyl]-2,3-dihydro-1H-naphtho[1,2-e][1,3,2]oxazaphos-
phinine [(RC,SC,SP)-L10]: Method A in Scheme 1. 1-((S)-Phenyl{[(R)-
1-phenylethyl]amino}methyl)naphthalen-2-ol (706.9 mg, 2.0 mmol,
1.0 equiv.) was dissolved in THF (10 mL) and the solution cooled to
–78 °C. Afterwards n-butyllithium (1.6
M in hexanes, 2.53 mL,
4.04 mmol, 2.02 equiv.) was added dropwise within 15 min, and the
mixture was stirred for 1 h at –78 °C and 1 h at room temperature.
The solution was cooled again to –78 °C, and a solution of phos-
phorus trichloride (175 μL, 2.0 mmol, 1.0 equiv.) in THF (6 mL) was
added dropwise within 15 min. The mixture was stirred for 1 h at
–78 °C and another 1.5 h at room temperature. In another Schlenk
flask 2-(diphenylphosphanyl)phenol (545.4 mg, 1.96 mmol,
0.98 equiv.) was dissolved in THF (10 mL), and TMEDA (300 μL,
2.0 mmol, 1.0 equiv.) was added. The solution was cooled to –78 °C,
133.95 (CH, Ar), 134.02 (CH, Ar), 134.06 (CH, Ar), 137.0 (d, JC,P
12.2 Hz, Cq, Ar), 137.1 (d, JC,P = 12.4 Hz, Cq, Ar), 141.5 (d, JC,P
=
=
6.2 Hz, Cq, Ar), 141.9 (Cq, Ar), 147.7 (d, JC,P = 9.0 Hz, Cq, Ar), 155.8
(dd, JC,P = 8.0, JC,P = 18.8 Hz, Cq, Ar) ppm. 31P{1H} NMR (162 MHz,
CDCl3): δ = –17.0 (d, JP, P = 19.3 Hz), 131.5 (d, JP, P = 19.3 Hz) ppm.
EI-MS: m/z (%) = 294.1 (10), 279.1 (22), 278.1 (100), 277.1 (46), 232.1
(12), 231.1 (33), 200.1 (13), 199.1 (58), 183.1 (38), 152.1 (12), 149.1
(15), 107.1 (12), 106.1 (93), 105.1 (32), 92.1 (31), 91.1 (45), 79.1 (19),
and n-butyllithium (1.6
M in hexanes, 1.25 mL, 2.0 mmol, 1.0 equiv.)
was added dropwise within 15 min. The mixture was stirred for 1 h
at –78 °C and 1 h at 0 °C. The solution was cooled again to –78 °C,
and the solution of the phosphoramidochloridite (RC,SC,RP)-2 was
added dropwise within 15 min. The mixture was stirred for 2 h at
–78 °C and then allowed to reach room temperature overnight.
All volatiles were removed at high vacuum, and the residue was
redissolved in THF (10 mL) and filtered through basic alumina. After
elution with THF (10 mL), all volatiles were removed under reduced
pressure to give a colorless solid. The residue was recrystallized
+
78.1 (12), 77.1 (27), 74.1 (10). HRMS (ESI): calcd. for C43H36NO2P2
[M + H]+ 660.22158; found 660.22207. [α]D25 = –50.5 (c = 0.5, CH2Cl2).
(1R,3S)-3-[2-(Diphenylphosphanyl)phenoxy]-1-phenyl-2-[(R)-1-
phenylethyl]-2,3-dihydro-1H-naphtho[1,2-e][1,3,2]oxazaphos-
phinine [(RC,RC,SP)-L10]: Method B in Scheme 1. To a solution of
phosphorus trichloride (357 μL, 4.08 mmol, 1.02 equiv.) in CH2Cl2
(8 mL) was added triethylamine (1.12 mL, 8.0 mmol, 2.0 equiv.), and
the solution was cooled to 0 °C. A solution of 2-(diphenylphos- from toluene/ethanol. The precipitate was collected, washed with
phanyl)phenol (1.113 g, 4.0 mmol, 1.0 equiv.) in CH2Cl2 (12 mL) was
added dropwise within 5 min, and the mixture was stirred for
small amounts of ethanol, and dried to yield the product as a color-
less solid. Yield: 287.0 mg (0.44 mmol, 22 %). 1H NMR (400 MHz,
Eur. J. Org. Chem. 2017, 4111–4116
4114
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim