Aminophosphane and Phosphoramidite Ligands Derived from Amino Acid Esters
benzyl), 128.83 (s, arom. CH of benzyl), 128.54 (d, JC,P = 11.8 Hz,
arom. CH of PPh2), 128.28 (s, arom. CH), 128.27 (d, JC,P = 8.8 Hz,
131.48 (s, quat. C), 130.90 (s, quat. C), 130.29 (s, arom. CH), 130.15
(s, arom. CH), 129.52 (d, JC,P = 1.2 Hz, arom. CH), 128.60 (s,
arom. CH of PPh2), 128.25 (s, arom. CH), 126.66 (s, arom. CH), 2ϫarom. CH), 128.44 (s, arom. CH), 128.39 (s, arom. CH), 127.12
2
3
69.32 [d, JC,P = 40.3 Hz, C(CO)], 50.96 (s, OCH3), 36.77 (d, JC,P
= 9.3 Hz, PhCH2), 32.57 (d, 2JC,P = 8.7 Hz, NCH3) ppm. 31P NMR
(121 MHz, C6D6): δ = 67.9 (s) ppm. MS (ESI-TOF): m/z (%) =
378.18 (88) [M + H]+. C23H24NO2P (377.42): calcd. C 73.2, H 6.4,
N 3.7; found C 73.1, H 6.5, N 3.6.
(s, arom. CH), 127.01 (s, arom. CH), 126.82 (s, arom. CH), 126.17
(s, 2ϫarom. CH), 124.90 (s, arom. CH), 124.73 (s, arom. CH),
123.97 (d, JC,P = 5.0 Hz, quat. C), 122.67 (d, JC,P = 1.9 Hz, quat.
C), 122.21 (s, arom. CH), 122.04 (s, arom. CH), 122.02 (s, arom.
2
CH), 61.99 [d, JC,P = 45.3 Hz, HC(CO)], 52.33 (s, OCH3), 34.96
3
2
(d, JC,P = 6.2 Hz, PhCH2), 28.23 (d, JC,P = 3.7 Hz, NCH3) ppm.
31P NMR (121 MHz, CDCl3): δ = 148.6 (s) ppm. MS (ESI-TOF):
m/z (%) = 530.16 (41) [M + Na]+. C31H26NO4P (507.52): calcd. C
73.4, H 5.2, N 2.8; found C 73.3, H 5.2, N 2.6.
Methyl (R)-2-(Methyldiphenylphosphanylamino)-3-phenylpropionate
[(RBn)-2b]: Compound (RBn)-2b was prepared according to the
above procedure from (RBn)-1b (2.480 g, 12.77 mmol). Yield:
4.240 g, 88%. [α]2D0 = +85.2 (c = 1.00, toluene). MS (ESI-TOF):
m/z (%) = 378.18 (100) [M + H]+. C23H24NO2P (377.42): calcd. C
73.2, H 6.4, N 3.7; found C 73.1, H 6.5, N 3.6.
Methyl
(S)-2-{N,N-Methyl-[(R)-(dinaphtho[2,1-d:1Ј,2Ј-f][1,3,2]di-
oxaphosphepin-2-yl)]amino}-3-phenylpropionate [(SBn,Rbin)-3d]: Pre-
pared according to the general procedure from (SBn)-1a (1.897 g,
9.77 mmol), diisopropylethylamine (1.262 g, 9.77 mmol, ca.
1.69 mL) and chloro-(R)-2,2Ј-O,OЈ-(1,1Ј-binaphthyl)phosphite
(3.440 g, 9.81 mmol). Yield: 3.400 g, 69%. [α]2D0 = –533.5 (c = 1.00,
toluene). NMR as for (RBn,Sbin)-3c. MS (ESI-TOF): m/z (%) =
530.16 (100) [M + Na]+. C31H26NO4P (507.52): calcd. C 73.4, H
5.2, N 2.8; found C 73.4, H 5.2, N 2.6.
General Procedure for the Synthesis of Phosphoramidites 3 and 4:
To a solution of MeNHCHR(CO2Me) (R = CH2Ph, Me) in tolu-
ene (30 mL) was added diisopropylethylamine (1 equiv.) and
chloro-(S or R)-2,2Ј-O,OЈ-(1,1Ј-binaphthyl)phosphite (1 equiv.).
The mixture was stirred overnight at r.t. before being filtered
through Al2O3. The solvent was removed in vacuo to afford the
product as a white solid.
Methyl (S)-2-{N,N-Methyl-[(S)-(dinaphtho[2,1-d:1Ј,2Ј-f][1,3,2]dioxa-
phosphepin-2-yl)]amino}-3-phenylpropionate [(SBn,Sbin)-3a]: Pre-
pared according to the general procedure from (SBn)-1a (1.000 g,
5.15 mmol), diisopropylethylamine (0.665 g, 5.15 mmol, ca.
0.89 mL) and chloro-(S)-2,2Ј-O,OЈ-(1,1Ј-binaphthyl)phosphite
Methyl
(S)-2-{N,N-Methyl-[(R)-(dinaphtho[2,1-d:1Ј,2Ј-f][1,3,2]di-
oxaphosphepin-2-yl)]amino}propionate [(SMe,Rbin)-4a]: Prepared ac-
cording to the general procedure from [(SMe)-1c]HCl (0.300 g,
1.95 mmol), diisopropylethylamine (0.530 g, 4.10 mmol, ca.
0.69 mL) and chloro-(R)-2,2Ј-O,OЈ-(1,1Ј-binaphthyl)phosphite
(1.806 g, 5.15 mmol). Yield: 1.502 g, 58%. M.p. 70–71 °C. [α]2D0
=
(0.720 g, 2.05 mmol). Yield: 0.767 g, 91%. M.p. 62–64 °C. [α]2D0
=
+281.2 (c = 0.26, toluene). 1H NMR (300 MHz, CDCl3): δ = 7.95–
7.73 (m, 4 H, arom. H), 7.48–7.15 (m, 12 H, arom. H), 6.66 (d,
–475.8 (c = 0.85, toluene). 1H NMR (300 MHz, CDCl3): δ = 7.98–
7.90 (m, 4 H, arom. H), 7.54 (d, JH,H = 8.8 Hz, 2 H, arom. H),
7.45–7.35 (m, 4 H, arom. H), 7.31–7.23 (m, 2 H, arom. H), 4.32
3
3
JH,H = 8.8 Hz, 1 H, arom. H), 4.53 [ddd, JA,X = 6.1 Hz, JB,X
=
3
3
3
9.8 Hz, JH,P = 11.5 Hz, 1 H, HC(CO)], 3.76 (s, 3 H, OCH3), 3.36
[dq, JH,H = 7.2 Hz, JH,P = 9.6 Hz, 1 H, HC(CO)], 3.84 (s, 3 H,
2
3
3
3
3
and 3.09 (ABX, JA,B = 14.4 Hz, JA,X = 6.1 Hz, JB,X = 9.8 Hz, 2
OCH3), 2.28 (d, JH,P = 4.8 Hz, 3 H, NCH3), 1.42 (d, JH,H
=
H, PhCH2), 2.23 (d, JHP = 4.0 Hz, 3 H, NCH3) ppm. 13C NMR
3
7.2 Hz, 3 H, CCH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 173.43
3
(d, 3JC,P = 3.1 Hz, C=O), 150.08–122.04 (arom. CЈs), 55.09 [d, 2JC,P
(75 MHz, CDCl3): δ = 172.41 (d, JC,P = 6.2 Hz, C=O), 149.67–
2
122.10 (arom. CЈs), 61.27 [d, JC,P = 43.4 Hz, HC(CO)], 52.35 (s,
OCH3), 35.51 (d, JC,P = 6.2 Hz, PhCH2), 28.64 (s, NCH3) ppm.
31P NMR (121 MHz, CDCl3): δ = 149.0 (s) ppm. MS (ESI-TOF):
m/z (%) = 530.16 (100) [M + Na]+. C31H26NO4P (507.52): calcd.
C 73.4, H 5.2, N 2.8; found C 73.5, H 5.3, N 2.6.
= 42.2 Hz, HC(CO)], 52.22 (s, OCH3), 28.10 (d, JC,P = 3.1 Hz,
NCH3), 16.08 (d, JC,P
(121 MHz, CDCl3): δ = 148.5 (s) ppm. MS (ESI-TOF): m/z (%) =
454.11 (91) [M + Na]+. C25H22NO4P (431.42): calcd. C 69.6, H 5.1,
N 3.3; found C 69.7, H 5.2, N 3.3.
3
=
6.8 Hz, CCH3) ppm. 31P NMR
Methyl (R)-2-{N,N-Methyl-[(R)-(dinaphtho[2,1-d:1Ј,2Ј-f][1,3,2]di-
oxaphosphepin-2-yl)]amino}-3-phenylpropionate [(RBn,Rbin)-3b]: Pre-
pared according to the general procedure from (RBn)-2b (1.560 g,
8.03 mmol), diisopropylethylamine (1.047 g, 8.10 mmol, ca.
1.40 mL) and chloro-(R)-2,2Ј-O,OЈ-(1,1Ј-binaphthyl)phosphite
(2.840 g, 8.10 mmol). Yield: 2.703 g, 66%. [α]2D0 = –285.3 (c = 1.00,
toluene). NMR as for (SBn,Sbin)-3a. MS (ESI-TOF): m/z (%) =
530.16 (100) [M + Na]+. C31H26NO4P (507.52): calcd. C 73.4, H
5.2, N 2.8; found C 73.4, H 5.4, N 2.6.
Methyl
(S)-2-{N,N-Methyl-[(S)-(dinaphtho[2,1-d:1Ј,2Ј-f][1,3,2]di-
oxaphosphepin-2-yl)]amino}propionate [(SMe,Sbin)-4b]: Prepared ac-
cording to the general procedure from [(SMe)-1c]HCl (0.581 g,
3.78 mmol), diisopropylethylamine (1.026 g, 7.94 mmol, ca.
1.33 mL) and chloro-(S)-2,2Ј-O,OЈ-(1,1Ј-binaphthyl)phosphite
(1.393 g, 3.97 mmol). Yield: 1.452 g, 89%. M.p. 61–63 °C. [α]2D0
=
1
+481.2 (c = 0.85, toluene). H NMR (300 MHz, CDCl3): δ = 7.97
(d, JH,H = 8.8 Hz, 1 H, arom. H), 7.93–7.87 (m, 3 H, arom. H),
7.53 (d, JH,H = 8.8 Hz, 1 H, arom. H), 7.44–7.38 (m, 4 H, arom.
3
Methyl
(R)-2-{N,N-Methyl-[(S)-(dinaphtho[2,1-d:1Ј,2Ј-f][1,3,2]di-
H), 7.34–7.21 (m, 3 H, arom. H), 4.24 [dq, 3JH,H = 7.2 Hz, JH,P
=
oxaphosphepin-2-yl)]amino}-3-phenylpropionate [(RBn,Sbin)-3c]: Pre-
pared according to the general procedure from (RBn)-1b (1.230 g,
6.33 mmol), diisopropylethylamine (0.818 g, 6.33 mmol, ca.
1.10 mL) and chloro-(S)-2,2Ј-O,OЈ-(1,1Ј-binaphthyl)phosphite
9.9 Hz, 1 H, HC(CO)], 3.74 (s, 3 H, OCH3), 2.33 (d, 3JH,P = 5.7 Hz,
3 H, NCH3), 1.51 (d, 3JH,H = 7.2 Hz, 3 H, CCH3) ppm. 13C NMR
3
(75 MHz, CDCl3): δ = 173.24 (d, JCP = 6.8 Hz, C=O), 149.80 (d,
JCP = 5.6 Hz, quat. C), 149.42 (s, quat. C), 132.89 (d, JC,P = 1.2 Hz,
quat. C), 132.69 (s, quat. C), 131.54 (s, quat. C), 130.87 (s, quat.
C), 130.44 (s, arom. CH), 130.02 (s, arom. CH), 128.46 (s, arom.
(2.230 g, 6.33 mmol). Yield: 1.502 g, 58%. M.p. 70–71 °C. [α]2D0
=
+542.6 (c = 1.00, toluene). 1H NMR (300 MHz, CDCl3): δ = 7.95–
7.89 (m, 4 H, arom. H), 7.46–7.19 (m, 13 H, arom. H), 4.48 [ddd, CH), 128.36 (s, arom. CH), 127.12 (s, arom. CH), 127.07 (s, arom.
JA,X = 5.5 Hz, JB,X = 10.0 Hz, JH,P = 11.6 Hz, 1 H, HC(CO)], 3.90 CH), 126.22 (s, arom. CH), 124.96 (s, arom. CH), 124.78 (s, arom.
(s, 3 H, OCH3), 3.29 and 3.01 (ABX, JA,B = 14.3 Hz, JA,X = 5.5 Hz, CH), 124.01 (d, JC,P = 5.0 Hz, quat. C), 122.69 (d, JC,P = 1.9 Hz,
JB,X = 10.0 Hz, 2 H, PhCH2), 2.26 (d, JHP = 3.2 Hz, 3 H, NCH3) quat. C), 122.12 (s, arom. CH), 122.09 (s, arom. CH), 122.07 (s,
3
2
ppm. 13C NMR (75 MHz, CDCl3): δ = 172.46 (d, JC,P = 5.0 Hz,
arom. CH), 55.14 [d, JC,P = 37.2 Hz, HC(CO)], 52.19 (s, OCH3),
3
2
C=O), 150.15 (d, JC,P = 5.6 Hz, quat. C), 149.32 (s, quat. C), 137.43
(s, quat. C), 132.85 (d, JC,P = 1.2 Hz, quat. C), 132.63 (s, quat. C),
28.79 (d, JC,P = 6.8 Hz, CCH3), 16.54 (d, JC,P = 6.2 Hz, NCH3)
ppm. 31P NMR (121 MHz, CDCl3): δ = 148.2 (s) ppm. MS (ESI-
Eur. J. Inorg. Chem. 2007, 4153–4161
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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