0.69 (t, 3H, J \ 7.2 Hz). 13C NMR (CDCl ): d 162.6, 162.1,
4.96 (q, 1H, J \ 1.6, oleÐnic CH), 4.60 (q, 1H, J \ 0.9 Hz, ole-
Ðnic CH), 2.23È1.86 (m, 4H), 1.56 (m, 3H), 1.41È1.31 (m, 7H)
and 0.78È0.74 (m, 9H). 13C NMR (C D ): d 161.5, 160.7,
158.4, 139.5, 119.1, 118.6, 110.9, 37.2, 32.1, 30.8, 30.2, 29.8, 28.1,
24.4, 22.6, 22.3 and 13.9. IR (neat): 2962, 2936, 2876, 1734 and
1456 cm~1. GC-MS: m/z (% relative intensity) 262 (M`, 16),
205 (4), 191 (73), 177 (18), 163 (25), 149 (28), 105 (27), 91 (83),
77 (75), 69 (22) and 55 (100).
3
160.3, 137.6, 128.6, 128.4, 127.4, 115.2, 112.9, 32.1, 28.6, 23.5,
21.2, 13.9 and 13.8. IR (KBr): 2968, 2936, 2876, 1711, 1628,
1539, 1390, 940, 899, 768 and 706 cm~1. GC-MS: m/z (% rela-
tive intensity) 256 (M`, 23), 228 (32), 199 (100), 157 (28), 128
6
6
(20) and 71 (50). Calc. for C
Found: C, 79.57; H, 7.89%.
H
O : C, 79.69; H, 7.81.
17 20
2
The reaction of methyl 3,6-dichloro-2-hexenoate with 4-
octyne. The reaction formed two products, 2g and 2g@, approx-
imately in a 1 : 2.7 ratio. Chromatography on alumina Ðrst
with hexane and then with a 5 : 95 (v/v) mixture of ethyl
acetate and hexane gave analytically pure samples of 2g (11.0
mg, 0.043 mmol, 9%) and 2g@ (38.1 mg, 17.3 mmol, 35%) both
as a pale yellow oil and a mixture of these.
Isomer 2i-B. 1H NMR (C D ): d 5.98 (s, 1H, oleÐnic CH),
6
6
4.98È4.95 (m, 2H, oleÐnic CH ), 2.15È1.95 (m, 4H), 1.79 (s,
2
3H), 1.16È1.04 (m, 7H) and 0.81È0.75 (m, 9H). 13C NMR
(C D ): d 161.0, 159.6, 159.5, 138.1, 118.6, 115.1, 112.9, 40.5,
6
6
31.9, 30.9, 28.6, 24.8, 22.7, 22.4, 21.5 and 13.9. IR (neat): 2960,
2932, 2874, 1734, 1543 and 1075 cm~1. GC-MS: m/z (% rela-
tive intensity) 262 (M`, 10), 205 (14), 191 (24), 177 (27), 163
(34), 150 (28), 107 (24), 91 (59), 79 (47), 69 (100) and 55 (69).
4-(3-Chloropropyl)-5,6-dipropyl-2H-pyran-2-one
2g.
1H
NMR (C D ): d 5.77 (s, 1H, oleÐnic CH), 2.91 (t, 2H, J \ 6.1),
HRMS: calc. for C
H
O m/z 262.1931, found 262.1925.
6
6
17 26
2
2.08 (t, 2H, J \ 7.3), 1.96 (t, 2H, J \ 7.7), 1.86 (t, 2H, J \ 8.1),
1.54È1.06 (m, 6H), 0.74 (t, 3H, J \ 7.3) and 0.73 (t, 3H, J \ 7.4
Hz). 13C NMR (C D ): d 161.4, 161.3, 157.7, 114.4, 111.7,
Palladium-catalysed cross-coupling of compound 1a with 1-
hexyne a†ording methyl 3-(n-butyl)-(Z)-2-nonen-4-ynoate 3.
The reaction was carried out under conditions similar to those
described for compound 2. After 5 h of heating, the reaction
mixture was similarly worked up. Chromatography on
alumina with hexane gave an oil (60.0 mg, 0.27 mmol, 54%),
which was distilled over Kugelrohr to furnish a pale yellow
oil; bath temperature 110 ¡C/1.2 Torr. 1H NMR (C D ): d
6
6
44.0, 32.8, 31.0, 29.1, 27.9, 24.1, 21.1, 14.0 and 13.8. IR (neat):
2966, 2936, 2876, 1725, 1632 and 1545 cm~1. GC-MS: m/z (%
relative intensity) 256 (M` for 35Cl isotope, 18), 228 (15), 199
(89), 166 (100), 151 (26), 123 (20), 107 (13), 91 (37), 71 (82) and
55 (57). Calc. for C
65.03; H, 8.35%.
H
ClO : C, 65.50; H, 8.19. Found: C,
14 21
2
6
6
4-(Cyclopropyl)-5,6-dipropyl-2H-pyran-2-one 2gº. 1H NMR
5.98 (s, 1H, C2CH), 3.44 (s, 3H), 2.24 (t, 2H, J \ 6.5), 2.06 (t,
2H, J \ 7.5 Hz) and 1.54È0.76 (m, 14H). 13C NMR (C D ): d
(C D ): d 5.61 (s, 1H, oleÐnic CH), 2.15È2.04 (m, 4H), 1.50 (m,
6
6
6
6
2H), 1.29È1.07 (m, 3H), 0.77 (t, 3H, J \ 7.4), 0.74 (t, 3H, J \ 7.4
Hz), 0.42 (m, 2H) and 0.25 (m, 2H). 13C NMR (C D ): d 161.9,
165.1, 140.6, 123.2, 103.3, 79.8, 50.6, 39.2, 30.6, 30.4, 22.2, 22.1,
19.9, 13.9 and 13.7. IR (neat): 2962, 2934, 2866, 2220, 1734,
1615, 1218, 1193 and 1154 cm~1. GC-MS: m/z (% relative
intensity) 222 (M`, 1), 193 (38), 180 (26), 165 (100), 151 (46),
138 (20), 105 (24), 91 (35), 77 (28) and 55 (28). HRMS: calc. for
6
6
160.8, 160.4, 115.2, 106.9, 33.8, 28.4, 23.7, 21.1, 14.1, 13.8, 12.7
and 9.1 (2C). IR (neat): 2964, 2936, 2876, 1721, 1632 and 1545
cm~1. GC-MS m/z (% relative intensity) 220 (M` for 35Cl
isotope, 35), 192 (28), 163 (100), 149 (24), 121 (30), 91 (48), 71
(79) and 55 (23).
C
H
O m/z 222.1619, found 222.1640.
14 22
2
Complex 4. A solution of compound 1a (35.2 mg, 0.2 mmol)
and Pd(PPh ) (115.4 mg, 0.1 mmol) in toluene (2.0 mL) was
stirred at 90 ¡C for 3 h. Removal of volatiles in vacuo followed
Reaction of compound 1a with 1-phenyl-1-butyne forming
isomeric 2h. The reaction formed two regioisomers 2h-A and
2h-B in a 1.2 : 1 ratio. Chromatography on alumina Ðrst with
hexane and then with a 5 : 95 (v/v) mixture of ethyl acetate
and hexane allowed isolation of analytically pure 2h-A (15.4
mg, 0.06 mmol, 12%) and 2h-B (20.5 mg, 0.08 mmol, 16%) as a
pale yellow oil in addition to mixture fractions.
3 4
by recrystallization from a tolueneÈhexane mixture gave ana-
lytically pure complex 4 (67.0 mg, 0.083 mmol, 83.0%) as a
white solid, mp 172.5È174.0 ¡C (decomp.). 1H NMR (CDCl ):
3
d 7.78È7.72 (m, 12H), 7.40È7.33 (m, 18H), 4.96 (s, 1H, oleÐnic
CH), 3.43 (s, 3H), 2.00 (t, 2H, J \ 7.3 Hz), 0.77È0.73 (m, 2H)
and 0.55È0.47 (m, 5H). 31P NMR (CDCl ): d 23.1. Calc. for
Isomer 2h-A. 1H NMR (CDCl ): d 7.44È7.37 (m, 3H), 7.15È
3
3
C
H
ClO P Pd: C, 65.51; H, 5.34; Cl, 4.34. Found: C,
7.12 (m, 2H), 6.06 (s, 1H, oleÐnic CH), 2.27È2.07 (m, 4H), 1.34È
44 43
2 2
65.41; H, 5.17; Cl, 4.11%.
1.08 (m, 7H) and 0.74 (t, 3H, J \ 7.2 Hz). 13C NMR (CDCl ):
3
d 163.1, 163.0, 160.8, 134.4, 130.1, 128.7, 128.0, 118.8, 110.1,
33.2, 30.1, 25.3, 22.1, 13.8 and 12.2. IR (neat): 2962, 2934, 2874,
1727, 1632, 1545, 768 and 704 cm~1. GC-MS: m/z (% relative
intensity) 256 (M`, 13), 214 (30), 186 (100), 171 (23), 128 (24)
Acknowledgements
We thank the Japan Science and Technology Corporation
(JST) for Ðnancial support through the CREST (Core
Research for Evolutional Science and Technology) program
and for a postdoctoral fellowship to R.H.
and 57 (68). Calc. for C
79.55; H, 7.90%.
H
O : C, 79.69; H, 7.81. Found: C,
17 20
2
Isomer 2h-B. 1H NMR (CDCl ): d 7.49È7.40 (m, 5H), 6.15
3
(s, 1H, oleÐnic CH), 2.49 (t, 2H, J \ 7.2), 2.40 (t, 2H, J \ 7.4),
1.64È1.37 (m, 4H), 1.07 (t, 3H, J \ 7.4) and 0.96 (t, 3H, J \ 7.2
References and notes
Hz). 13C NMR (CDCl ): d 162.4, 161.1, 157.7, 133.1, 129.6,
3
1
J. V. N. Vara Prasad, K. S. Para, E. A. Lunney, D. F. Ortwine,
J. B. Dunbar, Jr., D. Ferguson, P. J. Tummino, D. Hupe, B. D.
Tait, J. M. Domagala, C. Humblet, T. N. Bhat, B. Liu, D. M. A.
Guerin, E. T. Baldwin, J. W. Erickson and T. K. Sawyer, J. Am.
Chem. Soc., 1994, 116, 6989.
For synthesis and chemistry of 2H-pyran-2-ones, see: (a) L.
Staunton, in Comprehensive Organic Chemistry, ed. P. G.
Sammes, Pergamon Press, Oxford, 1979, vol. 4, p. 629; (b) G. P.
Ellis and J. D. Hepworth, in Comprehensive Heterocyclic Chem-
istry, ed. A. J. Boulton and A. Mckillop, Pergamon Press,
Oxford, 1984, vol. 3, p. 675.; (c) Other publications on the synthe-
sis:Y. Inoue, Y. Itoh and H. Hashimoto, Chem. L ett., 1977, 855;
(d) Y. Inoue, Y. Itoh and H. Hashimoto, Chem. L ett., 1978, 633;
(e) Y. Inoue, Y. Itoh, H. Kazama and H. Hashimoto, Bull. Chem.
Soc. Jpn., 1980, 53, 3329; ( f ) D. Walther, H. Schonberg and E.
Dinjus, J. Organomet. Chem., 1987, 334, 377; (g) T. Tsuda, T.
128.7, 128.3, 118.2, 112.3, 31.8, 30.8, 22.5, 19.8, 15.3 and 13.8.
IR (neat): 2962, 2934, 2876, 1727, 1630, 1543, 1062 and 698
cm~1. GC-MS: m/z (% relative intensity) 256 (M`, 24), 214
(49), 185 (91), 171 (23), 129 (12), 105 (84) and 77 (100).
2
Reaction of compound 1a with 2,7-dimethyl-1-octen-3-yne
forming 2i. The reaction formed two regioisomers 2i-A and
2i-B in a 1 : 1 ratio. Chromatography on alumina Ðrst with
hexane and then with a 2 : 98 (v/v) mixture of ethyl acetate
and hexane allowed isolation of analytically pure 2i-A (12.0
mg, 0.046 mmol, 9%) and 2i-B (22.2 mg, 0.085 mmol, 17%) as
a pale yellow oil in addition to mixture fractions.
Isomer 2i-A. 1H NMR (C D ): d 5.95 (s, 1H, oleÐnic CH),
6
6
New J. Chem., 2001, 25, 179È184
183