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P. Shanmugam, P. Rajasingh / Tetrahedron 60 (2004) 9283–9295
106.03, 126.89, 128.65, 128.78, 128.91, 130.38, 143.83.
Mass spectra m/z: 271 (MC). Elemental analysis: Calcd for
C18H25NO: C, 79.60%, H, 9.28%, N, 5.16%. Found: C,
79.63%, H, 9.23% N, 5.13%.
108.18, 117.04, 127.58, 129.00, 135.12, 138.00, 144.39.
Mass spectra m/z: 211 (MC). Elemental analysis:
C14H13NO, Calcd C, 79.59%, H, 6.20%, N, 6.63%.
Found: C, 79.55%, H, 6.21%, N, 6.60%.
3.4.5. Methyl (2E)-2-[(octyloxy)methyl]-3-phenylacryl-
ate (12q). Colourless oil; yield: 97%; IR(neat) nmax: 1601,
3.4.11. (2E)-3-(4-Methoxyphenyl)-2-[(prop-2-ynyloxy)-
methyl]acrylonitrile (9m). Colourless oil; yield: 72%;
IR(neat) nmax: 1600, 2100, 3300 cmK1; 1H NMR: d 2.48 (s,
1H), 3.83 (s, 3H), 4.25 (s, 2H), 4.32 (s, 2H), 7.00 (d, 2H, JZ
8.8 Hz), 7.09 (s, 1H), 7.74 (d, 2H, JZ8.8 Hz); 13C NMR: d
55.34, 57.45, 70.35, 75.66, 79.15, 105.01, 114.34, 118.12,
125.82, 130.94, 144.50, 161.52. Mass spectra m/z: 227
(MC). Elemental analysis: C14H13NO2: Calcd C, 73.99%,
H, 5.77%, N, 6.16%. Found: C, 73.95%, H, 5.79%, N,
6.10%;.
1
1622, 2214 cmK1; H NMR: d 0.88 (t, 3H, JZ6.93 Hz),
1.25 (m, 10H), 1.63 (m, 2H), 3.54 (t, 2H, JZ6.54 Hz), 3.83
(s, 3H), 4.26 (s, 2H), 7.39 (m, 3H), 7.53 (m, 2H), 7.9 (s, 1H);
13C NMR: d 14.14, 26.33, 27.71, 29.17, 29.35, 29.47, 29.77,
51.90, 64.81, 70.91, 128.29, 128.52, 129.36, 129.96, 134.88,
144.58, 167.42. Mass spectra m/z: 304 (MC). Elemental
analysis: Calcd for C19H28O3: C, 74.96%, H, 9.27%. Found:
C, 74.89%, H, 9.32%.
3.4.6. Ethyl (2E)-3-phenyl-2-[(prop-2-ynyloxy)methyl]
3.4.12. Methyl (2E)-3-phenyl-2-[(prop-2-ynyloxy)-
methyl]acrylate (9q). Colourless oil; yield: 95%; IR(neat)
nmax: 1600, 1715, 2100, 3300 cmK1; 1H NMR: d 2.42 (t, 1H,
JZ2.34 Hz), 3.84 (s, 3H), 4.26 (d, 2H, JZ2.34 Hz), 4.39 (s,
2H), 7.32 (m, 3H), 7.53 (m, 2H), 7.92 (s, 1H); 13C NMR: d
52.26, 58.08, 64.25, 74.70, 79.63, 128.51, 18.54, 129.55,
129.99, 134.51, 145.27, 167.98. Mass spectra m/z: 230
(MC). Elemental analysis: C14H14O3: Calcd C, 73.03%, H,
6.13%. Found: C, 73.00%, H, 6.12%.
acrylate (9a). Colourless oil; yield: 92%; IR(neat) nmax
:
1
1600, 1622, 1720, 2150, 3300 cmK1; H NMR: d 1.36 (t,
3H, JZ7.11 Hz), 2.4 (t, 1H, JZ2.34 Hz), 4.26 (d, 2H, JZ
2.34 Hz), 4.30 (q, 2H, JZ7.11 Hz), 4.37 (s, 2H), 7.38 (m,
3H), 7.55 (m., 2H), 7.89 (s, 1H); 13C NMR: d 14.29, 58.05,
61.09, 64.21, 74.64, 79.69, 128.30, 128.50, 129.44, 129.95,
134.58, 144.90, 167.45. Mass spectra m/z: 244 (MC).
Elemental analysis: Calcd for C15H16O3: C, 73.75%, H,
6.60%. Found: C, 73.80%, H, 6.63%.
3.4.13. Methyl (2E)-3-(4-chlorophenyl)-2-[(prop-2-ynyl-
oxy)methyl]acrylate (9r). Colourless oil; yield: 90%;
3.4.7. (2E)-3-Phenyl-2-[(prop-2-ynyloxy)methyl]acrylo-
1
nitrile (9b). Colourless oil; yield: 90%; IR(neat) nmax
:
IR(neat) nmax: 1600, 1710, 2100, 3300 cmK1; H NMR: d
1
1600, 1620, 2200, 3300 cmK1; H NMR: d 2.48 (s, 1H),
4.25 (s, 2H), 4.32 (s, 2H), 7.18 (s, 1H), 7.41 (m, 3H), 4.77
(m, 2H); 13C NMR: d 57.47, 70.35, 75.67, 79.10, 108.17,
117.01, 128.93, 129.10, 130.53, 132.95, 144.45. Mass
spectra m/z: 197 (MC). Elemental analysis: Calcd for
C13H11NO: C, 79.16%, H, 5.62, N, 7.10%. Found: C,
79.15%, H, 5.60% N, 7.13%.
2.42 (t, 1H, JZ2.3 Hz), 3.85 (s, 3H), 4.28 (d, 2H, JZ
2.34 Hz), 4.4 (s, 2H), 7.35 (d, 2H, JZ8.4 Hz), 7.5 (d, 2H,
JZ8.4 Hz), 7.84 (s, 1H); 13C NMR: d 52.08, 58.10, 64.20,
74.68, 79.64, 128.75, 129.42, 131.12, 133.17, 135.41,
143.03, 167.96. Mass spectra m/z: 264 (MC). HRMS:
Calcd for C14H13ClO3: 264.0553. Found: 264.0550.
3.4.14. Methyl (2E)-3-(4-methylphenyl)-2-[(prop-2-ynyl-
oxy)methyl]acrylate (9s). Colourless oil; yield: 85%;
3.4.8. Ethyl (2E)-3-(4-chlorophenyl)-2-[(prop-2-ynyl-
oxy)methyl]acrylate (9e). Colourless oil; yield: 91%;
1
IR(neat) nmax: 1600, 1710, 2100, 3300 cmK1; H NMR: d
IR(neat) nmax: 1600, 1622, 1712, 2150, 3305 cmK1
;
1H
2.32 (s, 3H), 2.42 (t, 1H, JZ2.3 Hz), 3.83 (s, 3H), 4.25 (d,
2H, JZ2.3 Hz), 4.39 (s, 2H), 7.14 (d, 2H, JZ7.8 Hz), 7.26
(d, 2H, JZ7.8 Hz), 7.9 (s, 1H); 13C NMR: d 42.08, 52.24,
58.10, 64.26, 74.68, 79.60, 127.80, 129.04, 134.54, 135.20,
138.10, 145.22, 167.89. Mass spectra m/z: 244 (MC).
Elemental analysis: C15H16O3: Calcd C, 73.75%, H, 6.60%.
Found: C, 73.70%, H, 6.57%.
NMR: d 1.36 (t, 3H, JZ7.11 Hz), 2.4 (t, 1H, JZ2.34 Hz),
4.25–4.32 (m, 4H), 4.35 (s, 2H), 7.35 (d, 2H, JZ8.4 Hz), 7.5
(d, 2H, JZ8.4 Hz), 7.83 (s, 1H); 13C NMR: d 14.29, 58.10,
61.12, 64.25, 74.61, 79.64, 128.77, 128.40, 130.98, 13.20,
135.45, 143.12, 167.42. Mass spectra m/z: 278 (MC).
HRMS: Calcd for C15H15ClO3: 278.0710. Found: 278.0701.
3.4.9. (2E)-3-(4-Chlorophenyl)-2-[(prop-2-ynyloxy)-
methyl]acrylonitrile (9f). Colourless oil; yield: 89%;
3.4.15. Methyl (2E)-3-(4-methoxyphenyl)-2-[(prop-2-
ynyloxy)methyl]acrylate (9t). Colourless oil; yield: 80%;
1
1
IR(neat) nmax: 1605, 2140, 3302 cmK1; H NMR: d 2.47
IR(neat) nmax: 1600, 1705, 2100, 3300 cmK1; H NMR: d
(t, 1H, JZ2.34 Hz), 4.28 (s, 2H), 4.30 (s, 2H), 7.19 (s, 1H),
7.38 (d, 2H, JZ8.4 Hz), 7.5 (d, 2H, JZ8.4 Hz); 13C NMR:
d 57.45, 70.32, 75.66, 79.10, 108.52, 117.12, 128.98,
130.02, 131.23, 136.36, 143.06. Mass spectra m/z: 231
(MC). HRMS: Calcd for C13H10ClO3: 231.0451. Found:
231.0450.
2.41 (t, 1H, JZ2.3 Hz), 3.78 (s, 3H), 3.83 (s, 3H), 4.24 (d,
2H, JZ2.3 Hz), 4.38 (s, 2H), 6.94 (d, 2H, JZ8.78 Hz), 7.75
(d, 2H, JZ8.78 Hz), 7.86 (s, 1H); 13C NMR: d 52.30, 55.43,
58.06, 64.20, 74.68, 79.62, 114.34, 125.82, 130.93, 134.40,
145.20, 161.51, 166.24. Mass spectra m/z: 260 (MC).
Elemental analysis: C15H16O4: Calcd C, 69.22%, H, 6.20%.
Found: C, 69.20%, H, 6.15%.
3.4.10. (2E)-3-(4-Methylphenyl)-2-[(prop-2-ynyloxy)-
methyl]acrylonitrile (9i). Colourless oil; yield: 86%;
3.5. Typical experimental procedure for radical
cyclization and protiodestannylation
1
IR(neat) nmax: 1600, 2145, 3300 cmK1; H NMR: d 2.34
(s, 3H), 2.42 (t, 1H, JZ2.3 Hz), 4.25 (s, 2H), 4.32 (s, 2H),
7.18 (s, 1H), 7.12 (d, 2H, JZ7.8 Hz), 7.22 (d, 2H, JZ
7.8 Hz); 13C NMR: d 42.10, 57.45, 70.40, 75.62, 79.13,
A mixture of alkenyl propargyl ether 6a (200 mg,
0.86 mmol), 1.5 equiv of freshly prepared tri-n-butyltin