10.1002/chem.201901694
Chemistry - A European Journal
FULL PAPER
Compound 39. Product 39 was obtained as a white spume following the
same acetalization procedure described above starting from hemiketal 38
(25 mg, 0.10 mmol). Yield: 29 mg, 96%. [α]D25= 20.1° (c= 0.50, 98% ee,
CH2Cl2). 1H NMR (300 MHz, CDCl3) δ 7.41–7.19 (m, 5H), 5.54 (d, J= 4.7
Hz, 1H), 4.04–3.87 (m, 2H), 3.73–3.61 (m, 3H), 2.80 (d, J= 10.7 Hz, 1H),
2.35–2.21 (m, 1H), 2.08–1.95 (m, 1H), 1.89 (d, J= 13.3 Hz, 2H), 1.74–
1.67 (m, 1H), 1.62–1.50 (m, 2H), 1.49–1.36 (m, 3H), 1.32–1.20 (m, 2H),
0.98 (t, J= 7.4 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 139.1, 128.0, 126.9,
126.4, 83.6, 79.0, 62.1, 61.7, 52.7, 28.7, 27.9, 22.7, 20.6, 18.8, 8.7. MS
(ESI, m/z) C18H27O5 [MH+]: calcd.: 307.1904, found: 307.1917.
Chem. 2014, 12, 3531-3543; c) Y. Yin, Z. Jiang, ChemCatChem 2017,
9, 4306-4318; d) X. Jusseau, L. Chabaud, C. Guillou, Tetrahedron 2014,
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10, 764-785.
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Reaction of 10A with nitrostyrene 2a to give 42a: Catalyst C10 (9 mg,
0.015 mmol) was added to a solution of ketone 10A (30 mg, 0.15 mmol)
and nitroolefin 3a (45 mg, 0.30 mmol) in CH2Cl2 at 0 °C. The resulting
solution was stirred until the reaction was completed as monitored by
TLC (48 h). Then the mixture was directly submitted to a flash column
chromatography (hexane/EtOAc 95:5) to afford the title compound.
Colourless oil. Yield: 41 mg, 78%. [α]D25= –123.4° (c= 1.00, 99% ee,
CH2Cl2). 1H NMR (300 MHz, CDCl3) δ 7.43–7.25 (m, 8H), 7.18 (dd, J=
7.4, 2.0 Hz, 2H), 6.18 (d, J= 4.0 Hz, 2H), 5.23 (dd, J= 13.0, 3.8 Hz, 1H),
4.64 (dd, J= 12.9, 11.4 Hz, 1H), 4.03 (dd, J= 11.3, 3.8 Hz, 1H), 2.88–2.73
(m, 1H), 2.45–2.21 (m, 2H), 2.08–1.91 (m, 1H), 1.76–1.57 (m, 4H). 13C
NMR (75 MHz, CDCl3) δ 212.6, 136.4, 135.8, 134.7, 129.5, 129.2, 128.9,
128.6, 128.4, 127.8, 126.3, 77.8, 56.5, 49.1, 39.7, 38.9, 28.1, 21.6. MS
(ESI, m/z) C22H24NO3 [MH+]: calcd.: 350.1756, found: 350.1761.
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Reaction of 10A with formaldehyde to give 45: Catalyst C10 (9 mg,
0.015 mmol) was added to a solution of ketone 10A (20 mg, 0.10 mmol)
and paraformaldehyde (30 mg, 1 mmol) in CH2Cl2 at room temperature.
The resulting solution was stirred until the reaction was completed as
monitored by TLC (16 h). Then the mixture was directly submitted to a
flash column chromatography (hexane/EtOAc 90:10), affording the titled
25
compound essentially pure. White foam. Yield: 18 mg, 79%. [α]D
=
20.7° (c= 0.50, 89% ee, CH2Cl2). 1H NMR (300 MHz, CDCl3) δ 7.38–
7.27 (m, 5H), 6.36 (d, J= 16.6 Hz, 1H), 6.14 (d, J= 16.6 Hz, 1H), 3.83 (d,
J= 11.4 Hz, 1H), 3.44 (d, J= 11.5 Hz, 1H), 2.64 (td, J= 13.8, 6.0 Hz, 1H),
2.49 (bs, 1H), 2.38–2.28 (m, 1H), 2.04 (m, 3H), 1.84 (m, 2H), 1.70 (m,
1H). 13C NMR (75 MHz, CDCl3) δ 214.9, 136.4, 133.2, 129.8, 128.6,
128.0, 126.3, 67.9, 57.3, 40.0, 34.6, 27.5, 21.5. MS (ESI, m/z) C15H19O2
[MH+]: calcd.: 231.1385, found: 231.1389.
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Acknowledgements
Finantial support was provided by the University of the Basque
Country UPV/EHU (UFI QOSYC 11/22, GIU18/159), and
Ministerio de Economía
y
Competitividad (MEC, Grant
CTQ2016-78487-C2), Spain, O.M. thanks MEC and I.U. to
Basque Government for fellowship. G.Z. and E.G.-B thank the
European Funding Horizon 2020-MSCA (ITN-EJD CATMEC
14/06-721223). We also thank SGiker (UPV/EHU) for providing
NMR, HRMS, X-Ray and computation resources.
Keywords: Brønsted bases • quaternary centers •
organocatalysis • dienolates • synthetic methods
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