Paper
Organic & Biomolecular Chemistry
(Ar), 80.5 (C3), 76.5 (C4), 65.5 (C5), 57.5 (Me), 55.7 (C2), 55.6
(Me), 41.7 (C6), [α]D 39.9° (c 1.0, CHCl3).]
C. Tysoe, D. J. Mahuran and S. G. Withers, J. Am. Chem.
Soc., 2012, 55, 2737.
The Boc-protected intermediate (50 mg; 0.15 mmol) was
treated with TFA (400 μl) in CH2Cl2 (4 ml containing 1% water)
and concentrated to give the title product 27 (60 mg,
quantitative).
6 J. O. Olsen, S. P. A. Sauer, C. M. Pedersen and M. Bols, Org.
Biomol. Chem., 2015, 13, 3116.
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9 The piperidinium ion is still destabilized by the electro-
negative substituent, but the axial configuration is relatively
more stabilized compared to the equatorial counterpart.
10 B. Bernet, U. Piantini and A. Vasella, Carbohydr. Res., 1990,
204, 11.
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1H NMR (500 MHz, D2O) δ 7.61–7.52 (m, 5H, Ar), 4.76 (d,
J = 1.9 Hz, 0H), 4.43 (dd, J = 3.1, 1.4 Hz, 1H), 3.83–3.74 (m,
3H), 3.62 (d, J = 2.3 Hz, 1H), 3.60–3.57 (m, 0H), 3.54 (d, J =
1.9 Hz, 3H), 3.18 (d, J = 1.9 Hz, 3H).
13C NMR (126 MHz, D2O) δ 163.1, 162.8 (CvO, TFA), 138.3
(Ar), 128.6 (Ar), 127.6 (Ar), 127.1 (Ar), 116.4 (q, J = 292 Hz, 1 C,
TFA), 80.9, 76.8, 65.9, 58.7 (Me), 56.9 (C1), 56.8 (Me), 42.6 (C6).
[α]D 23.8° (c 1.0, MeOH).
HRMS calculated for C13H20NO3
238.1439.
= 238.1438 found:
Acknowledgements
We acknowledge the Danish National Research Council (FNU)
and the University of Copenhagen for support.
13 In the carbohydrate studies it has been found that methyl
3,6-anhydroglucoside hydrolyzes 446 times faster than the
corresponding methyl α-D-glucoside, more than the
expected 100 times as estimated on the basis of σs values,
which is probably due to the fact that besides being
all axial the compound has one oxygen less. See:
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19 The difference of 1.3 is also perfectly in accordance with
the difference in base strength between benzylamine (pKa
9.34) and methylamine (pKa 10.66).
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Org. Biomol. Chem.
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