The Journal of Organic Chemistry
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7.27−7.30 (m, 2H); 13C NMR (CDCl3) δ 11.8, 16.2 (d, J = 6.4 Hz),
16.3 (d, J = 6.4 Hz), 30.6 (d, J = 12.7 Hz), 32.6 (d, J = 139.1 Hz), 41.9
(d, J = 3.6 Hz), 61.2 (d, J = 6.5 Hz), 61.4 (d, J = 6.5 Hz), 126.3, 127.6,
128.3, 144.4 (d, J = 8.4 Hz); 31P NMR (CDCl3) δ 30.5.
(CDCl3) δ 27.6; HRMS calcd for C17H19ClO5P [M + H]+ 369.0659,
found 369.0656.
Dimethyl 2-benzoyloxy-2-(4-bromophenyl)ethylphos-
phonate (15e):6h 88% ee; [α]24 −16.2 (c 1.0, CHCl3); HPLC
D
Diethyl 2-methyl-4-phenylbutylphosphonate (12):6a 91% ee;
conditions: Chiralcel IB, n-hexane/2-propanol = 90/10, flow rate =
1.0 mL/min, major enantiomer tR = 11.7 min; minor enantiomer tR =
14.2 min; 1H NMR (400 MHz, CDCl3) δ 2.40 (ddd, 1H, J = 5.8, 15.5,
18.8 Hz), 2.66 (ddd, 1H, J = 8.3, 15.5, 17.5 Hz), 3.63 (d, 3H, J = 7.2 Hz),
3.66 (d, 3H, J = 7.2 Hz), 6.25 (ddd, 1H, J = 5.9, 8.6, 8.6 Hz), 7.34 (d, 2H,
J = 8.5 Hz), 7.43−7.51 (m, 4H), 7.57 (t, 1H, J = 7.4 Hz), 8.06 (d, 2H, J =
7.1 Hz); 13C NMR (CDCl3) δ 32.5 (d, J = 140.8 Hz), 52.3 (d, J = 3.1
Hz), 52.5 (d, J = 2.7 Hz), 70.8, 122.5 128.2, 128.4, 129.6, 129.7, 131.8,
133.2, 138.8 (d, J = 10.5 Hz), 165.1; 31P NMR (CDCl3) δ 27.6.
Dimethyl 2-benzoyloxy-2-(β-naphthyl)ethylphosphonate
[α]28 −11.4 (c 0.50, CHCl3); HPLC conditions: Chiralcel OJ-H,
D
n-hexane/2-propanol = 98/2, flow rate = 0.7 mL min−1, major enan-
tiomer tR = 19.7 min; minor enantiomer tR = 22.4 min; 1H NMR (400
MHz, CDCl3) δ 1.12 (d, 3H J = 6.7 Hz,), 1.30 (t, 6H, J = 7.1 Hz),
1.56−1.67 (m, 2H), 1.73−1.88 (m, 2H), 1.94−1.99 (m, 1H), 2.58−
2.66 (m, 2H), 4.02−4.09 (m, 4H), 7.14−7.18 (m, 3H), 7.24−7.28 (m,
2H); 13C NMR (CDCl3) δ 16.4, 16.5, 20.8 (d, J = 7.5 Hz), 28.0 (d, J =
4.0 Hz), 32.7 (d, J = 138.0 Hz), 33.0, 40.0 (d, J = 13.6 Hz), 61.2 (d, J =
6.4 Hz), 61.3 (d, J = 5.8 Hz), 125.7, 128.2, 128.3, 142.2; 31P NMR
(CDCl3) δ 31.7.
(15f):6h 92% ee; [α]22 −38.8 (c 0.34, CHCl3); HPLC conditions:
D
Diethyl 1-phenylethylphosphonate (13):6i,j 83% ee; [α]28
Chiralcel IB, n-hexane/2-propanol = 90/10, flow rate = 1.0 mL/min,
major enantiomer tR = 15.5 min; minor enantiomer tR = 18.4 min; 1H
NMR (400 MHz, CDCl3) δ 2.52 (ddd, 1H, J = 5.4, 15.6, 18.9 Hz),
2.80 (ddd, 1H, J = 8.6, 17.1, 17.1 Hz), 3.62 (d, 3H, J = 11.7 Hz), 3.65
(d, 3H, J = 11.3 Hz), 6.50 (ddd, 1H, J = 5.5, 8.9, 8.9 Hz), 7.43−7.51
(m, 4H), 7.57 (t, 2H, J = 8.0 Hz), 7.81−7.87 (m, 3H), 7.94 (s, 1H),
8.11 (d, 2H, J = 7.2 Hz); 13C NMR (CDCl3) δ 33.2 (d, J = 140.6 Hz),
52.4, 52.6, 71.6, 123.8, 125.8, 126.4, 127.6, 128.1, 128.4, 128.7, 129.7,
129.9, 133.0, 133.1, 133.2, 137.0, 137.1, 165.2; 31P NMR (CDCl3) δ 28.2.
Dimethyl 2-benzoyloxypropanephosphonate (15g):6h 92%
D
+4.8 (c 0.10, CHCl3); HPLC conditions: chiralpak AD-H, n-hexane/
2-propanol = 98/2, flow rate = 0.5 mL/min (210 nm), minor
enantiomer tR = 26.2 min; major enantiomer tR = 30.6 min; 1H NMR
(400 MHz, CDCl3) δ 1.14 (t, 3H, J = 6.9 Hz), 1.27 (t, 3H, J = 6.9 Hz),
1.58 (dd, 3H, J = 18.5, 7.4 Hz), 3.19 (dq, 1H, J = 22.5, 7.4 Hz), 3.75−
4.11 (m, 4H), 7.22−7.36 (m, 5H); 13C NMR (CDCl3) δ 15.6 (d, J =
5.0 Hz), 16.3 (d, J = 5.6 Hz), 16.4 (d, J = 5.9 Hz), 38.6 (d, J = 136
Hz), 61.9 (d, J = 6.9 Hz), 62.4 (d, J = 6.9 Hz), 126.9, 128.3, 128.5 (d,
J = 6.5 Hz), 138.0 (d, J = 6.5 Hz); 31P NMR (CDCl3) δ 29.2.
Dimethyl 2-benzoyloxy-2-phenylethylphosphonate (15a):6h
93% ee; [α]28D −4.2 (c 0.60, CHCl3); HPLC conditions: Chiralcel OJ-
H, n-hexane/2-propanol = 91/9, flow rate = 1.0 mL/min, major enan-
ee; [α]20 +33.4 (c 0.70, CHCl3); HPLC conditions: Chiralcel OJ-H,
D
n-hexane/2-propanol = 90/10, flow rate = 1.0 mL/min, major enan-
tiomer tR = 10.6 min; minor enantiomer tR = 12.5 min; 1H NMR (400
MHz, CDCl3) δ 1.52 (d, 3H, J = 6.3 Hz), 2.16 (ddd, 1H, J = 7.0, 15.3,
18.6 Hz), 2.38 (ddd, 1H, J = 6.1, 15.3, 19.1 Hz), 3.73 (d, 3H, J = 8.9
Hz), 3.75 (d, 3H, J = 8.9 Hz), 5.43 (ddd, 1H, J = 6.4, 12.7, 12.7 Hz),
7.44 (t, 2H, J = 7.4 Hz), 7.56 (t, 1H, J = 7.4 Hz), 8.05 (d, 2H, J = 7.1
Hz); 13C NMR (CDCl3) δ 21.1 (d, J = 7.9 Hz), 32.3 (d, J = 140.1 Hz),
52.5, 52.5, 128.3, 129.5, 130.1, 133.0, 165.6; 31P NMR (CDCl3) δ 29.2.
Dimethyl 1-benzoyloxy-2-phenylethylphosphonate
1
tiomer tR = 26.0 min; minor enantiomer tR = 32.5 min; H NMR (400
MHz, CDCl3) δ 2.43 (ddd, 1H, J = 5.5, 15.5, 18.8 Hz), 2.70 (ddd, 1H, J =
6.5, 15.5, 17.2 Hz), 3.62 (d, 3H, J = 5.9 Hz), 3.64 (d, 3H, J = 5.9 Hz),
6.30 (ddd, 1H, J = 5.5, 6.5, 9.0 Hz), 7.30−7.58 (m, 8H), 8.10 (d, 2H, J =
7.1 Hz); 13C NMR (CDCl3) δ 32.1, 33.5, 52.3 (d, J = 6.8 Hz), 52.5 (d, J =
7.3 Hz), 71.4 (d, J = 2.2 Hz), 126.4, 128.4, 128.5, 128.7, 129.9, 133.1,
139.7 (d, J = 10.7 Hz), 165.2; 31P NMR (CDCl3) δ 28.1.
(17):6d−g 13% ee; [α]28 −16.6 (c 1.0, CHCl3); HPLC conditions:
D
Dimethyl 2-benzoyloxy-2-(4-methylphenyl)ethylphos-
Chiralcel OD-H, n-hexane/2-propanol = 90/10, flow rate = 1.0 mL/min
(210 nm), minor enantiomer tR = 10.4 min; major enantiomer tR =
phonate (15b):6h 96% ee; [α]25 −2.7 (c 0.60, CHCl3); HPLC
D
conditions: chiralcel IB, n-hexane/2-propanol = 90/10, flow rate =
1.0 mL/min, major enantiomer tR = 9.6 min; minor enantiomer tR =
11.2 min; 1H NMR (400 MHz, CDCl3) δ 2.33 (s, 1H) 2.41 (ddd, 1H,
J = 5.4, 15.5, 18.8 Hz), 2.70 (ddd, 1H, J = 8.6, 17.1, 17.1 Hz), 3.62 (d,
3H, J = 5.5 Hz), 3.65 (d, 3H, J = 5.5 Hz), 6.27 (ddd, 1H, J = 5.5, 8.8,
8.8 Hz), 7.20 (d, 2H, J = 8.0 Hz), 7.35 (d, 2H, J = 8.0 Hz), 7.43 (t, 2H,
J = 7.5 Hz), 7.55 (t, 1H, J = 7.5 Hz), 8.07 (d, 2H, J = 7.1 Hz); 13C
NMR (CDCl3) δ 21.1, 32.2 (d, J = 140.2 Hz), 52.3 (d, J = 6.5 Hz),
52.5 (d, J = 7.7 Hz), 71.3, 126.4, 128.3, 129.3, 129.7, 130.0, 133.0,
136.8 (d, J = 10.9 Hz), 138.3, 165.2; 31P NMR (CDCl3) δ 28.2.
Dimethyl 2-benzoyloxy-2-(4-methoxyphenyl)ethylphos-
1
19.4 min; H NMR (400 MHz, CDCl3) δ 3.19−3.28 (m, 1H), 3.32−
3.38 (m, 1H), 3.77 (d, 3H, J = 10.7 Hz), 3.78 (d, 3H, J = 10.7 Hz),
5.77 (ddd, 1H, J = 12.2, 7.4 Hz, 4.0 Hz), 7.15−7.27 (m, 5H), 7.42 (t,
2H, J = 7.9 Hz), 7.56 (t, 1H, J = 7.4 Hz), 8.0 (d, 2H, J = 7.1 Hz). 13C
NMR (CDCl3) δ 35.7, 53.2 (d, J = 6.3 Hz), 53.4 (d, J = 8.8 Hz), 68.5
(d, J = 166 Hz), 126.9, 128.4, 128.5, 129.0, 129.1, 129.7, 133.3, 136.0
(d, J = 13.7 Hz), 165.0 (d, J = 4.5 Hz). 31P NMR (CDCl3) δ 22.5.
Dimethyl 2-acetylamino-2-phenylethylphosphonate
(19):6b,c 33% ee; [α]28 −10.5 (c 0.12, CHCl3); HPLC conditions:
D
Chiralcel OD-H, n-hexane/2-propanol = 85/15, flow rate = 0.5 mL/min,
1
minor enantiomer tR = 21.5 min; major enantiomer tR = 25.5 min; H
phonate (15c):6h 93% ee; [α]25 −2.1 (c 0.10, CHCl3); HPLC
D
NMR (400.0 MHz, CDCl3) δ 2.02 (s, 3H), 2.23−2.46 (m, 2H), 3.37 (d,
3H, J = 11.0 Hz,), 3.67 (d, 3H, J = 11.0 Hz), 5.39 (ddd, 1H, J = 23.9, 13.3,
7.2 Hz), 7.09 (br s, 1H), 7.25−7.37 (m, 5H); 13C NMR (CDCl3) δ
23.2, 31.7 (d, J = 139 Hz), 48.5 (d, J = 4.3 Hz), 52.1 (d, J = 6.7 Hz),
52.3 (d, J = 6.8 Hz), 126.0, 127.5, 128.6, 141.0 (d, J = 8.2 Hz), 169.4;
31P NMR (CDCl3) δ 29.7.
conditions: Chiralcel IB, n-hexane/2-propanol = 90/10, flow rate =
1.0 mL/min, major enantiomer tR = 14.8 min; minor enantiomer tR =
17.6 min; 1H NMR (400 MHz, CDCl3) δ 2.42 (ddd, 1H, J = 5.8, 15.5,
18.7 Hz), 2.70 (ddd, 1H, J = 8.3, 15.5, 17.5 Hz), 3.62 (d, 3H, J =
7.3 Hz), 3.65 (d, 3H, J = 7.3 Hz), 3.79 (s, 3H), 6.27 (ddd, 1H, J = 5.9,
8.5, 8.5 Hz), 6.87−6.91 (m, 2H), 7.39−7.45 (m, 4H), 7.53−7.57
(m, 1H), 8.07 (d, 2H, J = 7.1 Hz); 13C NMR (CDCl3) δ 32.6 (d, J =
140.0 Hz), 52.3 (d, J = 3.1 Hz), 52.5 (d, J = 2.7 Hz), 55.2 (d, J = 3.2 Hz)
71.1 (d, J = 2.6 Hz), 114.0, 128.0, 128.3, 129.7, 130.1, 131.9 (d, J = 10.3
Hz), 133.0, 159.6, 165.2; 31P NMR (CDCl3) δ 28.2.
ASSOCIATED CONTENT
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S
* Supporting Information
1H and 13C NMR spectra for new ClickFerrophos II ligands
L3−L5 and chiral phosphonate compounds; crystallographic
data for L4 (CIF). This material is available free of charge via
Dimethyl 2-benzoyloxy-2-(4-chlorophenyl)ethylphos-
phonate (15d): 94% ee; [α]27 −15.5 (c 1.0, CHCl3); HPLC
D
conditions: Chiralcel IB, n-hexane/2-propanol = 90/10, flow rate =
1.0 mL/min, major enantiomer tR = 11.2 min; minor enantiomer tR =
13.4 min; 1H NMR (400 MHz, CDCl3) δ 2.40 (ddd, 1H, J = 5.8, 15.5,
18.8 Hz), 2.66 (ddd, 1H, J = 8.2, 15.6, 17.5 Hz), 3.63 (d, 3H, J =
7.0 Hz), 3.65 (d, 3H, J = 7.0 Hz), 6.27 (ddd, 1H, J = 6.0, 8.6, 8.6 Hz),
7.33 (d, 2H, J = 8.5 Hz), 7.40−7.47 (m, 4H), 7.57 (t, 1H, J = 7.4 Hz),
8.06 (d, 2H, J = 7.1 Hz); 13C NMR (CDCl3) δ 32.5 (d, J = 140.9 Hz),
52.4 (d, J = 6.4 Hz), 52.5 (d, J = 6.4 Hz), 70.8, 127.9 128.4, 128.8,
129.6, 129.7, 133.2, 134.3, 138.3 (d, J = 10.4 Hz), 165.1; 31P NMR
AUTHOR INFORMATION
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Corresponding Author
Notes
The authors declare no competing financial interest.
3323
dx.doi.org/10.1021/jo300129m | J. Org. Chem. 2012, 77, 3318−3324