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Organic & Biomolecular Chemistry
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residue was purified by flash chromatography on silica gel (PE/EA =
Chem., 2014, 485.
DOI: 10.1039/C6OB02523D
2/3) to give 5 (14.6 mg, 41%) as a colorless oil that solidified on
4
For some recent examples, see: (a) H.-C. Xu, S. Chowdhury
and J. A. Ellman, Nat. Protoc. 2013, 8, 2271; (b) X.-Y. Chen, L.-
25
18
standing. []D = -42.1 (c 0.15, CH2Cl2) {lit.22b [α]D = -41 (c 1.0,
CH2Cl2); lit.22d [α]D25 = -41.2 (c 1.0, CH2Cl2)}; 1H NMR (600 MHz, CDCl3,
rotamers) δ 7.37– 7.29 (m, 2H), 7.25– 7.22 (m, 1H), 7.21– 7.17 (m,
2H), 5.13 (d, J = 11.4, 1H), 4.31 (d, J = 8.4, 1H), 3.90-3.81 (m, 1H),
3.73-3.65 (m, 1H), 3.41 (dd, J = 13.8, 2.4 Hz, 1H), 3.25-3.18 (m, 1H),
2.91 (dd, J = 18.0, 4.8 Hz, 1H), 2.86 (s, 2H), 2.82 (d, J = 11.4, 1H),
2.80 (s, 1H), 2.65-2.62 (m, 1H), 2.36-2.25 (m, 1H), 2.03-1.99 (m, 1H),
1.96-1.88 (m, 1H), 1.28 – 1.24 (m, 10H), 1.17 (d, J = 7.2 Hz, 3H), 0.89
(d, J = 7.2 Hz, 3H), 0.78 (d, J = 6.6 Hz, 1H), 0.55 (d, J = 7.2 Hz, 2H),
0.23 (d, J = 6.6 Hz, 2H), 0.19 (d, J = 7.2 Hz, 1H) ppm; 13C NMR (150
MHz, CDCl3, rotamers) δ 172.9, 172.1, 170.4, 170.1, 168.9, 168.7,
137.6, 131.1, 129.9, 129.4, 129.1, 129.0, 128.6, 127.2, 126.6, 83.0,
76.7, 76.0, 74.0, 70.5, 70.4, 61.5, 58.7, 41.2, 40.8, 40.7, 37.2, 36.6,
35.5, 31.9, 31.8, 31.6, 30.7, 30.3, 29.8, 29.5, 29.4, 29.2, 29.1, 29.0,
28.2, 26.2, 25.5, 22.8, 19.8, 18.4, 17.7, 16.9, 14.2, 12.2, 10.9 ppm;
HRMS (ESI-Orbitrap) m/z: [M + H]+ Calcd for C28H44NO6: 490.3163
found: 490.3166.
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Acknowledgements
Liu and X.-W. Sun, Tetrahedron Lett., 2016, 57, 2147; (p) S.
Zhao, G. Sirasani, S. Vaddypally, M. J. Zdilla and R. B. Andrade,
Tetrahedron, 2016, 72, 6107.
We thank the National Natural Science Foundation of China
(21472022, 21272041, 21072034) and the China Postdoctoral
Science Foundation (KLF301012) for financial support. The
authors thank Dr. Han-Qing Dong (Arvinas, Inc.) for helpful
suggestions. The authors also thank Dr. Wei Huang and Mr.
Xiao-Yun Wei for trying the method to asymmetric synthesis of
hapalosin.
5
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