10.1002/ejoc.201800051
European Journal of Organic Chemistry
FULL PAPER
(3R)-2-(3-(3,4-Dimethoxyphenyl)-2-((trityloxy)methyl)-2,3-
Acknowledgements
dihydrobenzo[b][1,4]dioxin-6-yl)-3-hydroxy-5,7-dimethoxychroman-
4-one (33): 32 (1 eq., 297 mg, 0.567 mmol) was coevaporated three
times with anhydrous THF and dissolved in anhydrous pyridine (2.14 mL).
Triphenylmethyl chloride (1.68 eq., 270 mg, 0.952 mmol) was added to
the solution and the solution was then heated at 50 °C for 15 h. The
reaction was monitored by TLC (EtOAc/Petroleum Ether 9:1). The
mixture was then diluted with MeOH and concentrated under reduced
pressure. The crude was next purified on a silica gel column eluting with
EtOAc/Petroleum Ether 6:4 in the presence of 1% of Et3N to
EtOAc/Petroleum Ether 8:2 + 1% of Et3N , affording 33 (314 mg, 0.41
mmol, 72 %) as a pale amorphous solid. Mp = 139-142 °C. Optical
This work was supported by the CNRS and the University of
Strasbourg. MMP and FS thank the French Ministry of research
for a PhD fellowship and L. G. A.-M the Erasmus program.
Robin Weiss is acknowledged for assistance with synthetic work.
The authors express their gratitude to Jean-Marc Weibel for
fruitful discussions.
Keywords: alcohol deoxygenation • molecular iodine • transition
metal-free • carbohydrates • steroids
20
1
rotation [α]D = -4 (c 0.9, CHCl3). H- NMR (400 MHz, CDCl3): δ 2.76
(dd, J = 10.6, 2.9 Hz, 1H, H19a), 3.56 (dd, J = 10.6, 2.1 Hz, 1H, H19b),
3.70 (s, 3H, H27), 3.80 (s, 3H, H1), 3.86 (s, 3H, H25), 3.93 (s, 3H, H5),
4.05−4.13 (m, 2H, H18, OH), 4.47 (ddd, J = 12.2, 5.7, 1.3 Hz, 1H, H10),
4.98 (d, J = 12.2 Hz, 1H, H11), 5.29 (d, J = 8.6 Hz, 1H, H20), 6.08−6.15
(m, 2H, H8, H3), 6.69 (d, J = 8.0 Hz, 1H, HAr), 6.81−6.87 (m, 2H, HAr),
7.13 (d, J = 3.5 Hz, 2, HAr), 7.17−7.30 (m, 10H, HAr), 7.43 (d, J = 8.1 Hz,
6H, HAr). 13C- NMR (100 MHz, CDCl3): δ 55.9 (C25, C27), 56.1, 56.4
(C1, C5), 63.1 (C19), 72.8 (C10), 76.7 (C20), 77.9 (C18), 83.1 (C11),
86.7 (C29), 93.4, 93.8 (C3, C8), 103.1 (C6), 110.4 (C17), 110.1 (C14),
116.6 (C13), 117.5 (CIIIAr), 120.4 (CIIIAr), 121.2 (CIIIAr), 123.9 (C12), 127.2,
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127.9, 128.8 (CIV Trityl), 129.6 (C21), 143.8 (C30, C31, C32), 144.1
Ar
(CIVAr), 144.7 (CIVA), 149.1 (C26), 149.4 (C24), 162.3 (CIVAr), 165.1 (C7),
167.1 (CIVAr), 191.0 (C9). IR (CHCl3) νmax : 3439, 2935, 1674, 1608, 1574,
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HRMS m/z [M+H]+ calcd for C47H43O10 767.2851; Found 767.2807.
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dimethoxyphenyl)prop-2-en-1-one (35): Compound 33 (1 eq., 95.2 mg,
0.124 mmol) was solubilized in dry toluene (0.53 mL). PPh3 (1.53 eq.,
49.7 mg, 0.189 mmol), pyridine (1 eq., 0.01 mL, 0.124 mmol) and iodine
(0.524 eq., 16.5 mg, 0.065 mmol) were successively added. The solution
was heated to 60 °C for 28 h. After completion, the reaction was cooled
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phase were separated. Brown residue was dissolved with CH2Cl2 and
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Aqueous phases were gathered and extracted three times with CH2Cl2.
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evaporated under reduced pressure. The residue was purified by flash
column chromatography on silica gel (EtOAc/Petroleum Ether 3:7 +1%
Et3N) to afford deoxygenated product 35 (45.5 mg, 0.0606 mmol, 49 %)
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as
[α]D
a
yellow foam. Mp
=
155-160 °C Optical rotation
20
= -2 (c 0.8, CHCl3). 1H-NMR (400 MHz, CDCl3): δ 2.80 (dd, J =
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10.8, 3.2 Hz, 1H, H19a), 3.55 (dd, J = 10.8, 2.4 Hz, 1H, H19b), 3.70 (s,
3H, OMe), 3.83 (s, 3H, H1), 3.87 (s, 3H, OMe), 3.90 (s, 3H, H5), 4.17 (dt,
J = 8.0, 2.6 Hz, 1H, H18), 5.27 (d, J = 8.1 Hz, 1H, H20), 5.96 (d, J = 2.3
Hz, 1H, H3), 6.11 (d, J = 2.3 Hz, 1H, H8), 6.74 (d, J = 8.5 Hz, 1H, H23),
6.85−6.90 (m, 2H, H28, H22), 7.08 (d, J = 8.4 Hz, 1H, H14), 7.20−7.24
(m, 4H, H13, Hpara), 7.25−7.29 (m, 6H, Hortho), 7.30 (d, J = 2.0 Hz, 1H,
H17), 7.40−7.45 (m, 6H, Hmeta), 7.76 (d, J = 15.5Hz, 1H, H11 or H10),
7.80 (d, J = 15.5 z, 1H, H10 or H11), 14.39 (s, 1H, OH). 13C-NMR (100
MHz, CDCl3): δ 55.7, 55.9, 56.0, 56.1 (C1, C5, C25, C27), 63.0 (C19),
76.9 (C20), 78.2 (C18), 86.8 (C29), 91.3 (C3), 93.9 (C8), 106.5 (C6),
110.6 (C28), 111.2 (C23), 116.6 (C17), 117.6 (C14), 120.3 (C22), 123.3
(C13), 125.8 (C10), 127.2 (Cpara), 127.9 (Cortho), 128.4 (C21), 128.7
(Cmeta), 129.3 (C12), 142.6 (C11), 143.7 (C30, C31, C32), 144.2 (C16),
145.9 (C15), 149.1 (C24), 149.6 (C26), 162.6 (C4), 166.2 (C2), 168.5
(C7), 192.6 (C9). IR (CHCl3) νmax : 2933, 1618, 1581, 1558, 1503, 1263,
1217, 1157, 1114, 1029, 817, 749, 701, 632 cm-1. HRMS m/z [M+H]+
calcd for C47H43O9 751.2902; Found 751.2902.
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