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D. Strzelecka et al.
Paper
Synthesis
H), 2.13–2.16 (m, 1 H), 1.89–1.92 (m, 1 H), 1.64–1.70 (m, 2 H), 1.36–
1.50 (m, 1 H), 1.18–1.28 (m, 1 H), 0.75–1.02 (m, 2 H), 0.93 (d, JP,H = 6.0
Hz, 3 H), 0.88 (d, JP,H = 6.6 Hz, 3 H), 0.47 (d, JP,H = 6.9 Hz, 3 H);
δ (minor) = 8.02–8.09 (m, 1 H), 7.68–7.79 (m, 2 H), 7.47–7.53 (m, 1
H), 7.39–7.46 (m, 3 H), 7.30–7.35 (m, 1 H), 7.16–7.22 (m, 1 H), 4.38–
4.39 (m, 1 H), 2.36 (s, 3 H), 2.25–2.28 (m, 1 H), 1.89–1.92 (m, 1 H),
1.64–1.70 (m, 3 H), 1.36–1.50 (m, 1 H), 1.18–1.28 (m, 1 H), 0.75–1.02
(m, 2 H), 0.95 (d, JP,H = 7.3 Hz, 3 H), 0.83 (d, JP,H = 6.0 Hz, 3 H), 0.67 (d,
JP,H = 6.3 Hz, 3 H).
13C NMR (CDCl3, 126 MHz): δ (major) = 141.6 (d, JP,C = 12.7 Hz), 134.1
(d, JP,C = 132.6 Hz), 132.8 (d, JP,C = 8.2 Hz), 132.0 (d, JP,C = 2.7 Hz), 131.6
(d, JP,C = 2.7 Hz), 131.4 (d, JP,C = 10.9 Hz), 131.3 (d, JP,C = 11.8 Hz), 130.4
(d, JP,C = 136.2 Hz), 128.3, 128.2 (d, JP,C = 11.8 Hz), 125.3 (d, JP,C = 12.7
Hz), 48.8, 43.7, 34.0, 31.5, 25.4, 22.6, 21.9, 21.3, 21.0, 15.2;
δ (minor) = 141.9 (d, JP,C = 12.7 Hz), 133.0 (d, JP,C = 133.5 Hz), 132.9 (d,
JP,C = 8.2 Hz), 132.1 (d, JP,C = 2.7 Hz), 131.7 (d, JP,C = 2.7 Hz), 131.4 (d,
JP,C = 10.9 Hz), 131.3 (d, JP,C = 11.8 Hz), 130.7 (d, JP,C = 136.2 Hz), 128.3,
128.2 (d, JP,C = 11.8 Hz), 125.3 (d, JP,C = 12.7 Hz), 48.8, 43.7, 34.0, 31.5,
25.4, 22.6, 21.9, 21.3, 21.0, 15.2.
L-Menthyl Benzylphenylphosphinate (17e; Mixture of Diastereo-
mers)
Prepared according to the general procedure from methyl benzyl-
phenylphosphinate (9g; 0.122 g, 0.49 mmol), L-menthol (0.116 g, 0.74
mmol), and n-BuLi (0.49 mL, 0.84 mmol); yield: 0.099 g (54%, 64%
de); Rf = 0.67 (EtOAc/hexane 9:1); GC: tR = 13.76 min (major) and tR =
13.87 min (minor).
1H NMR (CDCl3, 500 MHz): δ (major) = 7.61–7.69 (m, 2 H), 7.46–7.53
(m, 1 H), 7.36–7.43 (m, 2 H), 7.17–7.25 (m, 3 H), 7.10–7.17 (m, 2 H),
3.98–4.07 (m, 1 H), 3.32 (d, JP,H = 17.7 Hz, 2 H), 2.15–2.22 (m, 1 H),
1.87–1.94 (m, 1 H), 1.56–1.63 (m, 2 H), 1.29–1.40 (m, 2 H), 1.10–1.20
(m, 1 H), 0.76–1.02 (m, 2 H), 0.87 (d, JP,H = 6.3 Hz, 3 H), 0.81 (d,
JP,H = 7.3 Hz, 3 H), 0.37 (d, JP,H = 6.9 Hz, 3 H); δ (minor) = 7.61–7.69 (m,
2 H), 7.46–7.53 (m, 1 H), 7.36–7.43 (m, 2 H), 7.17–7.25 (m, 3 H), 7.10–
7.17 (m, 2 H), 4.24–4.33 (m, 1 H), 3.24 (dd, JH,H = 9.1 Hz, JP,H = 17.0 Hz,
2 H), 2.32–2.36 (m, 1 H), 1.95–2.00 (m, 1 H), 1.70–1.76 (m, 2 H), 1.29–
1.40 (m, 2 H), 1.10–1.20 (m, 1 H), 0.76–1.02 (m, 2 H), 0.87 (d, JP,H = 7.3
Hz, 3 H), 0.81 (d, JP,H = 7.3 Hz, 3 H), 0.73 (d, JP,H = 6.3 Hz, 3 H).
13C NMR (CDCl3, 126 MHz): δ (major) = 132.0 (d, JP,C = 10.6 Hz), 131.8
(d, JP,C = 7.7 Hz), 130.14 (d, JP,C = 5.4 Hz), 130.08 (d, JP,C = 2.7 Hz), 128.2,
128.1 (d, JP,C = 14.2 Hz), 126.6 (d, JP,C = 6.4 Hz), 48.8, 43.7, 38.8 (d,
JP,C = 97.2 Hz), 34.0, 31.5, 25.4, 22.6, 21.9, 21.0, 15.2; δ (minor) = 132.0
(d, JP,C = 10.6 Hz), 131.8 (d, JP,C = 7.7 Hz), 130.14 (d, JP,C = 5.4 Hz), 130.08
(d, JP,C = 2.7 Hz), 128.2, 128.1 (d, JP,C = 14.2 Hz), 126.6 (d, JP,C = 6.4 Hz),
48.8, 43.1, 38.8 (d, JP,C = 97.2 Hz), 34.0, 31.4, 25.4, 22.7, 21.9, 21.0, 15.5.
31P NMR (CDCl3, 202 MHz): δ (major) = 29.4; δ (minor) = 28.8.
MS (EI, 70 eV): m/z (%) = 234 (14), 233 (100), 232 (59), 231 (56), 215
(11), 213 (9), 165 (8), 141 (8), 95 (11), 91 (8), 81 (8).
HRMS (ESI-TOF): m/z [M + H]+ calcd for C23H31O2P: 371.2127; found:
371.2134.
31P NMR (CDCl3, 202 MHz): δ (major) = 37.8; δ (minor) = 37.1.
L-Menthyl tert-Butylphenylphosphinate (17d; Mixture of Diaste-
reomers)
MS (EI, 70 eV): m/z (%) = 234 (14), 233 (100), 232 (59), 231 (56), 215
(11), 213 (9), 165 (8), 141 (8), 95 (11), 91 (8), 81 (8).
HRMS (ESI-TOF): m/z [M + H]+ calcd for C20H31O2P: 393.1944; found:
393.1954.
Prepared according to the general procedure from tert-butylphenyl-
phosphinic chloride (9e; 0.108 g, 0.50 mmol), L-menthol (0.117 g,
0.75 mmol), and n-BuLi (0.50 mL, 0.85 mmol); yield: 0.134 g (80%,
69% de); Rf = 0.71 (EtOAc/hexane 9:1); GC: tR = 13.16 min (major) and
tR = 13.21 min (minor).
The data are in accordance with those previously reported in the lit-
erature.42
1H NMR (CDCl3, 500 MHz): δ (major) = 7.77–7.85 (m, 2 H), 7.50–7.56
(m, 1 H), 7.42–7.48 (m, 2 H), 4.01–4.10 (m, 1 H), 2.46–2.53 (m, 1 H),
2.11–2.21 (m, 1 H), 1.72–1.83 (m, 1 H), 1.57–1.70 (m, 2 H), 1.35–1.49
(m, 1 H), 1.18–1.28 (m, 1 H), 1.13 (d, JP,H = 15.5 Hz, 9 H), 0.75–1.04 (m,
2 H), 0.90 (d, JP,H = 6.0 Hz, 3 H), 0.89 (d, JP,H = 6.6 Hz, 3 H), 0.48 (d,
JP,H = 6.9 Hz, 3 H); δ (minor) = 7.77–7.85 (m, 2 H), 7.50–7.56 (m, 1 H),
7.42–7.48 (m, 2 H), 4.29–4.37 (m, 1 H), 2.36–2.44 (m, 1 H), 1.72–1.83
(m, 1 H), 1.57–1.70 (m, 3 H), 1.35–1.49 (m, 1 H), 1.18–1.28 (m, 1 H),
1.11 (d, JP,H = 12.9 Hz, 9 H), 0.75–1.04 (m, 2 H), 0.97 (d, JP,H = 7.3 Hz, 3
H), 0.87 (d, JP,H = 6.0 Hz, 3 H), 0.71 (d, JP,H = 6.3 Hz, 3 H).
13C NMR (CDCl3, 126 MHz): δ (major) = 133.2 (d, JP,C = 8.2 Hz), 131.8
(d, JP,C = 2.7 Hz), 129.4 (d, JP,C = 113.5 Hz), 127.9 (d, JP,C = 10.9 Hz), 55.0,
49.1, 43.8, 34.1, 32.9 (d, JP,C = 101.7 Hz), 31.6, 25.4, 24.4, 22.6, 22.0,
21.2, 15.4; δ (minor) = 133.2 (d, JP,C = 8.2 Hz), 131.6 (d, JP,C = 2.7 Hz),
129.4 (d, JP,C = 113.5 Hz), 127.9 (d, JP,C = 10.9 Hz), 49.1, 43.2, 34.1, 32.9
(d, JP,C = 101.7 Hz), 31.4, 25.4, 24.4, 22.6, 21.9, 21.2, 15.4.
Supporting Information
Supporting information for this article is available online at
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References
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Wiley-VCH: Weinheim, 2008.
(2) Catalytic Asymmetric Synthesis; Ojima, I., Ed.; Wiley-VCH: Wein-
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(3) Knowles, W. S.; Sabacky, M. J.; Vineyard, B. D.; Weinkauff, D. J.
J. Am. Chem. Soc. 1975, 97, 2567.
31P NMR (CDCl3, 202 MHz): δ (major) = 48.4; δ (minor) = 47.6.
MS (EI, 70 eV): m/z (%) = 200 (11), 199 (100), 143 (19), 142 (12), 139
(11), 95 (11), 83 (37), 81 (13), 57 (19), 55 (16).
HRMS (ESI-TOF): m/z [M + H]+ calcd for C20H33O2P: 337.2295; found:
(4) (a) Lipkowitz, K. B.; D’Hue, C. A.; Sakamoto, T.; Stack, J. N. J. Am.
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Russell, M. J. H. J. Chem. Soc., Perkin Trans. 1 1993, 831.
(c) Maienza, F.; Spindler, F.; Thommen, M.; Pugin, B.; Malan, C.;
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337.2291.
The data are in accordance with those previously reported in the lit-
erature.41
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–K