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M. Utaka, J. Org. Chem., 1998, 63, 1102.
8. M. Takadoi, K. Yamaguchi, and S. Terashima, Bioorg. Med. Chem., 2003, 11, 1169.
9. B. H. Lipshutz and C. Hackmann, J. Org. Chem., 1994, 59, 7437.
10. K. Matsumoto, K. Koyachi, and M. Shindo, Tetrahedron, 2013, 69, 1043.
11. Determined based on the NOESY spectrum.
12. The stereochemistry was tentatively assigned based on mechanistic consideration.
13. Determined based on the 1H NMR spectrum.
14. Compound 14: a clear oil. [α]D25 –14.6 (c 1.97, CHCl3); 1H NMR (400 MHz, CDCl3) δ 5.80-5.70 (m,
2H), 5.38-5.08 (m, 4H), 4.03 (td, J = 8.6, 3.6 Hz, 1H), 3.01 (m, 1H), 2.38-2.21 (m, 2H), 2.1 (m, 1H),
13
1.89-1.80 (m, 1H), 1.65-1.5 (m, 1H), 1.02 (t, J = 7.4 Hz, 3H); C NMR (100 MHz, CHCl3) δ 176,
134, 132, 120, 118, 84, 50, 46, 35, 27, 10; FTIR (neat) 3079, 2973, 2928, 1773, 1642, 1179 cm-1;
HRMS (EI) calcd for C11H16O2 (M+) 180.1150, found 180.1149.
15. For a similar ring closing metathesis, see: H. Miyaoka, Y. Hara, I. Shinohara, T. Kurokawa, and Y.
Yamada, Tetrahedron Lett., 2005, 46, 7945.
16. This compound was correlated to the known TBS ether5b by a three-step conversion (i, PivCl,
pyridine, CH2Cl2; ii, TBSCl, imidazole, DMF; iii, DIBAL-H, CH2Cl2, –78 °C), confirming its
absolute structure. The enantiomeric purity was determined to be 94% ee by 1H NMR analysis of the
corresponding R- and S-MTPA esters of the above-mentioned TBS ether derivative.
17. J. Inanaga, K. Hirata, H. Saeki, T. Katsuki, and M. Yamaguchi, Bull. Chem. Soc. Jpn., 1979, 52,
1989.
18. Compound 5: a clear oil. [α]D28 –113.2 (c 1.11, CHCl3) (lit.5b [α]D28 –68.3 (c 0.98, CHCl3)); 1H NMR
(400 MHz, CDCl3) δ 5.85-5.66 (m, 3H), 5.49-5.47 (m, 1H), 5.01-4.91 (m, 5H), 3.21 (br s, 1H), 2.47
(dddd, J = 16.0, 8.0, 4.0, 2.0 Hz, 1H), 2.27 (t, J = 7.6 Hz, 2H), 2.23-2.22 (m, 1H), 2.03 (m, 3H), 1.59
(m, 3H), 1.28 (m, 9H), 0.87 (t, J = 7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 174.0, 143.0, 140.0,
134.0, 130.0, 115.0, 114.0, 78.1, 53.0, 48.0, 36.0, 35.0, 34.0, 29.3, 29.3, 29.01, 29.0, 26.0, 25.0, 9.0;
FTIR (neat) 2929, 2856, 1733, 1639, 1459, 1377, 1246, 1175, 1098 cm-1; HRMS (EI) m/z calcd for
C20H32O2 (M+) 304.2402, found 304.2400.
19. Compound 3: a yellow oil. [α]D28 +11.0 (c 0.34, CHCl3) (lit.5b [α]D25 +12.9 (c 0.6, CHCl3)) (lit.2a [α]D
+14.5 (c 0.55, CHCl3)); 1H NMR (500 MHz, CDCl3) δ 4.88 (m, 1H), 3.44 (d, J = 2.5 Hz, 1H), 3.31
(d, J = 2.0 Hz, 1H), 2.37 (m, 2H), 2.13 (t, J = 7.8 Hz, 1H), 1.91-1.82 (m, 3H), 1.82-1.67 (m, 2H),
13
1.67-1.53 (m, 1H), 1.51-1.21 (m, 15H), 0.81 (t, J = 7.5 Hz, 3H ); C NMR (125 MHz, CDCl3) δ
173.8, 79.1, 61.4, 57.1, 44.3, 39.1, 33.7, 29.1, 28.6, 26.1, 25.8, 25.4, 25.0, 24.9, 24.9, 24.4, 24.3, 8.8;
FTIR (neat) 2936, 2857, 1731, 1456, 1363, 1219, 1174, 1084 cm-1; HRMS (EI) m/z calcd for
C18H30O3 (M+) 294.2195, found 294.2198.