1188
M. Shi et al. / Tetrahedron 59 (2003) 1181–1189
HRMS (EI) m/z 177.0786 (Mþ), C10H11O2N requires M,
177.0788].
(Mþ299, 100). [Found: HRMS (EI) m/z 157.1216 (Mþ1)þ,
C9H17O2 requires Mþ1, 157.1229].
3.2.15. Compound 3i. 25 mg, 10%; a colorless oil. IR (KBr)
n 2930, 1714 (CvO), 896 cm21
3.2.19. Compound 4a. The title compound was prepared in
the same manner as that described above.
;
1H NMR (CDCl3,
300 MHz, TMS) d 2.16 (3H, s, Me), 2.32 (3H, s, Me),
2.68–2.74 (2H, m, CH2), 3.59–3.65 (1H, m), 3.67–3.77
(1H, m), 5.88 (1H, s, CH), 6.21 (1H, s, CH), 6.25 (1H,
s, CH), 7.20–7.28 (1H, m, Ar), 7.68 (1H, dd, J¼9.6,
3.6 Hz, Ar), 8.5 (1H, d, J¼3.6 Hz, Ar), 8.56 (1H, s, Ar);
MS (EI) m/z 230 (Mþ217, 1.6), 176 (Mþ271, 93.1),
134 (Mþ2113, 49.7), 43 (Mþ2204, 100). [Found:
HRMS (EI) m/z 247.1216 (Mþ), C14H17O3N requires M,
247.1208].
94 mg, 80%; a colorless oil. IR (KBr) n 3486 (O–H), 2939,
1672 (CvO), 1517, 855 cm21; 1H NMR (CDCl3, 300 MHz,
TMS) d 1.01 (3H, t, J¼7.1 Hz, CH3), 2.70 (2H, q, J¼7.1 Hz,
CH2), 3.44 (1H, d, J¼5.9 Hz, OH), 5.68 (1H, d, J¼5.9 Hz,
CH), 6.03 (1H, s), 6.29 (1H, s), 7.52 (1H, dd, J¼7.8, 7.8 Hz,
Ar), 7.76 (1H, d, J¼7.8 Hz, Ar), 8.16 (1H, d, J¼7.8 Hz, Ar),
8.23 (1H, s, Ar); MS (EI) m/z 234 [(M2H)þ, 40.2], 218
(Mþ217, 100), 206 (Mþ229, 40.7), 188 (Mþ247, 57.9).
[Found: HRMS (EI) m/z 218.0838 (Mþ217), C12H12O3N
requires M217, 218.0817].
Compounds 1j and 2j (syn and anti mixture) were prepared
in the same manner as that described above.
3.2.20. Compound 4b. 95 mg, 81%; a colorless oil. IR
3.2.16. Compound 1j. 58 mg, 57%. IR (KBr) n 3438
(O–H), 2924, 1672 (CvO), 1575, 852 cm21
(KBr) n 3459 (O–H), 2938, 1672 (CvO), 1526, 808 cm21
;
;
1H NMR
1H NMR (CDCl3, 300 MHz, TMS) d 1.08 (3H, t, J¼7.1 Hz,
CH3), 2.70 (2H, q, J¼7.1 Hz, CH2), 3.44 (1H, s, OH), 5.60
(1H, s, CH), 6.06 (1H, s), 6.11 (1H, s), 7.08 (1H, dd, J¼6.8,
5.2 Hz, Ar), 7.30 (1H, d, J¼7.8 Hz, Ar), (1H, dd, J¼7.8,
7.8 Hz, Ar), (1H, d, J¼4.8 Hz, Ar); MS (EI) m/z 234
[(M2H)þ, 38.0], 218 (Mþ217, 100), 206 (Mþ229, 66.8),
188 (Mþ247, 31.5). [Found: HRMS (EI) m/z 218.0769
(Mþ217), C12H12O3N requires M217, 218.0817].
(CDCl3, 300 MHz, TMS) d 2.40 (3H, s, Me), 3.10 (1H, d,
J¼5.9 Hz, OH), 5.69 (1H, t, J¼5.9 Hz, CH), 6.13 (1H, s),
6.17 (1H, s), 6.31 (1H, dd, J¼16.3, 6.2 Hz, CH), 6.68 (1H, d,
J¼16.3 Hz), 7.26–7.41 (5H, m, Ar); MS (EI) m/z 202 (Mþ,
42.5), 184 (Mþ218, 50.3), 70 (Mþ2132, 66.2), 43
(Mþ2159, 100). [Found: HRMS (EI) m/z 202.1006 (Mþ),
C13H14O2 requires M, 202.0994].
3.2.17. Compound 2j. 33 mg, 24%.
3.2.21. Compound 4c. 48 mg, 41%; a colorless oil. IR
(KBr) n 3454 (O–H), 2938, 1675 (CvO), 1522, 835 cm21
;
syn-2j. IR (KBr) n3442 (O–H), 2938, 1676 and 1709
1
1H NMR (CDCl3, 300 MHz, TMS) d 1.07 (3H, t, J¼7.3 Hz,
CH3), 2.56 (1H, s, OH), 2.70 (2H, q, J¼7.1 Hz, CH2), 5.71
(1H, s, CH), 6.12 (1H, s), 6.20 (1H, s), 7.42 (1H, td, J¼7.8,
1.2 Hz, Ar), 7.62 (1H, td, J¼7.8, 1.2 Hz, Ar), 7.90 (1H, dd,
J¼7.8, 1.2 Hz, Ar), 8.0 (1H, dd, J¼7.8, 1.2 Hz, Ar); MS (EI)
m/z 218 (Mþ217, 1.9), 161 (Mþ274, 23.8), 104 (Mþ2131,
38.5), 57 (Mþ2178, 100). [Found: HRMS (EI) m/z
218.0802 (Mþ217), C12H12O3N requires M-17, 218.0817].
(CvO), 831 cm21; H NMR (CDCl3, 300 MHz, TMS) d
2.18 (3H, s, Me), 2.30 (3H, s, Me), 2.60 (1H, dd, J¼7.0,
7.0 Hz, CH), 2.64 (1H, dd, J¼7.0, 7.0 Hz, CH), 2.99–3.11
(1H, m, CH), 4.28 (1H, d, J¼2.2 Hz, OH), 4.50 (1H, dd,
J¼2.2, 2.0 Hz, CH), 5.87 (1H, s), 5.91 (1H, s), 6.29 (1H, dd,
J¼16.4, 6.2 Hz), 6.64 (1H, d, J¼16.4 Hz), 7.28–7.41 (5H,
m, Ar); MS (EI) m/z 272 (Mþ, 0.6), 255 (Mþ217, 35.6), 211
(Mþ261, 27.0), 125 (Mþ2147, 44.0), 43 (Mþ2229, 100).
[Found: HRMS (EI) m/z 273.1492 (Mþ1)þ, C17H21O3
requires Mþ1, 273.1491].
3.2.22. Compound 6. 47 mg, 40%; a colorless oil. IR (KBr)
1
n 3452 (O–H), 2980, 1688 (CvO), 880 cm21; H NMR
(CDCl3, 300 MHz, TMS) d 1.07 (3H, d, J¼7.3 Hz, CH3),
3.39 (1H, q, J¼7.3 Hz, CH), 3.50 (1H, br., s, OH), 5.72 (1H,
d, J¼2.0 Hz, CH), 6.13 (1H, dd, J¼9.8, 1.6 Hz, CH), 6.35
(1H, dd, J¼17.5, 1.6 Hz, CH), 6.45 (1H, dd, J¼17.5, 9.8 Hz,
CH), 7.42 (1H, td, J¼7.8, 1.2 Hz, Ar), 7.62 (1H, td, J¼7.8,
1.2 Hz, Ar), 7.90 (1H, dd, J¼7.8, 1.2 Hz, Ar), 8.0 (1H, dd,
J¼7.8, 1.2 Hz, Ar); MS (EI) m/z 186 (Mþ246, 1.1), 152
(Mþ283, 20.0), 104 (Mþ2131, 100), 87 (Mþ2151, 90.4).
[Found: HRMS (EI) m/z 235.034 (Mþ), C12H13O4N requires
M, 235.0845].
anti-2j. IR (KBr) n 3442 (O–H), 2938, 1676 and 1709
1
(CvO), 831 cm21; H NMR (CDCl3, 300 MHz, TMS) d
2.19 (3H, s, Me), 2.33 (3H, s, Me), 2.50 (1H, dd, J¼7.0,
7.0 Hz, CH), 2.58 (1H, dd, J¼7.0, 7.0 Hz, CH), 2.8 (1H, d,
J¼6.2 Hz, OH), 2.99–3.11 (1H, m, CH), 4.37 (1H, dd,
J¼7.4, 6.2 Hz, CH), 6.07 (1H, s), 6.10 (1H, s), 6.29 (1H, dd,
J¼16.4, 6.2 Hz), 6.64 (1H, d, J¼16.4 Hz), 7.28–7.41 (5H,
m, Ar); MS (EI) m/z 272 (Mþ, 0.6), 255 (Mþ217, 35.6), 211
(Mþ261, 27.0), 125 (Mþ2147, 44.0), 43 (Mþ2229, 100).
[Found: HRMS (EI) m/z 273.1492 (Mþ1)þ, C17H21O3
requires Mþ1, 273.1491].
3.2.23. Compound 4g. 79 mg, 83%; a colorless oil. IR
(KBr) n 3366 (O–H), 2938, 1675 (CvO), 1569, 857 cm21
;
3.2.18. Compound 1k. The title compound was prepared in
the same manner as that described above.
1H NMR (CDCl3, 300 MHz, TMS) d 1.03 (3H, t, J¼7.3 Hz,
CH3), 2.68 (2H, q, J¼7.3 Hz, CH2), 4.85 (1H, d, J¼4.1 Hz,
OH), 5.69 (1H, d, J¼4.1 Hz, CH), 6.08 (1H, s), 6.19 (1H, s),
7.18 (1H, dd, J¼7.6, 4.9 Hz, Ar), 7.45 (1H, d, J¼7.8 Hz,
Ar), 7.68 (1H, dd, J¼7.6, 6.0 Hz, Ar), 8.50 (1H, d,
J¼4.9 Hz, Ar); MS (EI) m/z 192 [(MH)þ, 61.1], 174
(Mþ217, 87.4), 162 (Mþ229, 93.8), 108 (Mþ283, 100).
[Found: HRMS (EI) m/z 174.0934 (Mþ217), C11H12ON
requires M-17, 174.0919].
20 mg, 15%; a colorless oil. IR (KBr) n 3420 (O–H), 1712
1
(CvO), 830 cm21; H NMR (CDCl3, 300 MHz, TMS) d
0.89 (3H, t, J¼7.7 Hz, CH3), 1.25–1.54 (4H, m, CH2),
1.55–1.70 (2H, m, CH2), 2.12 (3H, s, CH3), 2.74 (1H, br., s,
OH), 4.35–4.47 (1H, m, CH), 6.0 (1H, s, CH), 6.10 (1H, s,
CH); MS (EI) m/z 156 (Mþ, 1.1), 97 (Mþ259, 100), 57