Total Synthesis of All Stereoisomers of Thiamphenicol
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NMR (300 MHz, [D6]acetone): δ = 7.89 (d, J = 8.4 Hz, 2 H), 7.69
(d, J = 8.4 Hz, 2 H), 7.54 (d, J = 8.7 Hz, 1 H), 6.38 (s, 1 H), 5.30
(br. s, 1 H), 5.18 (br. s, 1 H), 4.27 (br. s, 1 H), 4.17–4.13 (m, 1 H),
3.80 (t, J = 10.3 Hz, 1 H), 3.68 (dd, J = 10.3, 5.2 Hz, 1 H), 3.08 (s, 3
H) ppm. 13C NMR (75 MHz, [D6]acetone): δ = 164.5, 149.6, 141.0,
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127.9, 127.8, 71.3, 67.5, 62.1, 58.0, 44.4 ppm. IR (neat): ν = 3489,
˜
3443, 3252, 2920, 1692, 1559, 1276, 1139, 770 cm–1. MS (CI, NH3):
m/z = 373.09 [M + NH4]+.
(1S,2S)-1: Yield 72%, m.p. 161–163 °C; ref.[1a] m.p. 164–167 °C. Rf
= 0.19 (CH2Cl2/MeOH, 9:1). [α]2D0 = –9.2 (c = 0.25, MeOH). 1H
NMR (300 MHz, [D6]acetone): δ = 7.89 (d, J = 8.4 Hz, 2 H), 7.69
(d, J = 8.4 Hz, 2 H), 7.56 (d, J = 8.6 Hz, 1 H), 6.38 (s, 1 H), 5.30
(s, 1 H), 5.20 (s, 1 H), 4.29 (s, 1 H), 4.18–4.12 (m, 1 H), 3.80 (t, J
= 7.9 Hz, 1 H), 3.68 (dd, J = 10.0, 5.0 Hz, 1 H), 3.08 (s, 3 H) ppm.
13C NMR (75 MHz, [D6]acetone): δ = 164.5, 149.6, 140.9, 127.9,
127.8, 71.2, 67.5, 62.1, 58.0, 44.4 ppm. IR (neat): ν = 3489, 3448,
˜
3252, 2916, 1687, 1563, 1280, 1143, 774 cm–1. MS (CI, NH3): m/z
= 373.10 [M + NH4]+.
Supporting Information (see footnote on the first page of this arti-
cle): NMR spectra of 1, 4–6, and 9 as well as SFC chromatograms
of 4 and 9.
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Acknowledgments
The authors thank the Agence Nationale de la Recherche (ANR)
(ANR-11-BS07-017-02) for financial support (ANR STIMAS,
2011–2014, grant to P.-G. E.).
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