5544 J . Org. Chem., Vol. 65, No. 18, 2000
Avery et al.
23.0, 37.1, 60.4, 127.9, 128.5, 128.8, 133.1, 136.6, 140.1, 167.9,
198.5; MS m/z (%) 246 (M+, 10), 200 (32), 172 (25), 105 (100);
HRMS of titled compound, C15H18O3 calcd, 246.1256; found,
246.1262. The corresponding (Z)-isomer was left uncharacter-
ized as a result of insufficient material being isolated, while
the characterization of the (E) and (Z)-3-[4-(2-oxo-2-p h en yl-
eth yl)-1,3-d ioxola n -2-yl]-1-p h en yl-1-p r op a n on es has been
reported elsewhere.44
tr a n s-(()-Ben zyl 2-(2-ben zoyl-3-m eth ylcyclop r op yl)-
a ceta te (7a ): Rf 0.37 (4:1 hexane/ethyl acetate); mp 54.5-56
°C (heptane); IR 1726, 1659, 1171 cm-1; 1H NMR (CDCl3, 600
MHz) δ 1.21 (d, J ) 6.6 Hz, 3H), 1.87 (ddq, J ) 10.8, 6.6, 4.4
Hz, 1H), 2.08 (dddd, J ) 10.8, 7.8, 6.8, 4.4 Hz, 1H), 2.26 (dd,
J ) 4.4, 4.4 Hz, 1H), 2.52 (dd, J ) 16.1, 7.8 Hz, 1H), 2.61 (dd,
J ) 16.1, 6.8 Hz, 1H), 5.12 (s, 2H), 7.29-7.30 (m, 5H), 7.43-
7.46 (m, 2H), 7.53-7.56 (m, 1H), 7.93-7.95 (m, 2H); 13C NMR
(CDCl3, 150 MHz) δ 10.1, 22.2, 24.1, 30.3, 30.5, 64.2, 125.7,
125.9, 126.0, 126.2, 126.3, 130.4, 133.5, 135.8, 169.8, 196.9;
MS m/z (%) 308 (M+, 5), 217 (37), 105 (84), 91 (100). Anal.
Calcd for C20H20O3 (308.4): C, 77.90; H, 6.54. Found: C, 78.04;
H, 6.52.
cis-(()-Ben zyl 2-(2-ben zoyl-3-m eth ylcyclop r op yl)a ce-
ta te (12a ): Rf 0.42 (4:1 hexane/ethyl acetate); IR (neat) 1737,
1664, 1597, 1578, 1448, 1213, 1168 cm-1; 1H NMR (CDCl3, 600
MHz) δ 1.21 (d, J ) 6.0 Hz, 3H), 1.83 (ddq, J ) 8.8, 8.8, 6.0
Hz, 1H), 1.93 (dddd, J ) 8.8, 8.8, 7.8, 6.8 Hz, 1H), 2.80 (dd, J
) 8.8, 8.8 Hz, 1H), 2.91 (dd, J ) 17.6, 6.8 Hz, 1H), 2.99 (dd, J
) 17.6, 7.8 Hz, 1H), 5.08 and 5.10 (ABq, J ) 12.6 Hz, 2H),7.28-
7.33 (m, 5H), 7.42-7.46 (m, 2H), 7.53-7.56 (m, 1H), 7.90-
7.94 (m, 2H); 13C NMR (CDCl3, 150 MHz) δ 7.3, 22.0, 23.1,
24.3, 27.8, 66.1, 127.7, 128.0, 128.4, 128.5, 128.7, 132.3, 136.1,
139.8, 173.1, 199.5. The titled compound (12a ) was found to
be unstable at ambient temperature undergoing an enolene
rearrangement over several days to afford 16. See below for
characterization of 16.
5.11 (ABq, J ) 13.2 Hz, 2H), 7.26-7.29 (m, 5H), 7.67-7.69
(m, 2H), 8.00-8.02 (m, 2H); 13C NMR (CDCl3, 150 MHz) δ 12.5,
25.1, 27.8, 32.8, 32.9, 66.6, 123.7 (q, J ) 271 Hz), 125.5 (q, J
) 3.5 Hz), 128.2, 128.3, 128.3, 128.5, 133.9 (q, J ) 33 Hz),
135.6, 140.6, 171.9, 198.3; MS m/z (%) 376 (M+, 1), 358 (2),
285 (18), 173 (33), 145 (13), 91 (100). Anal. Calcd for C21H19F3O3
(376.4): C, 67.02; H, 5.09. Found: C, 66.97; H, 5.11.
cis-(()-Ben zyl 2-{2-m eth yl-3-[4-(tr iflu or om eth yl)ben -
zoyl]cyclop r op yl}a ceta te (13a ): Rf 0.55 (4:1 hexane/ethyl
acetate). The titled compound (13a ) was found to be unstable
at ambient temperature undergoing an enolene rearrangement
over several days to afford 17. See below for characterization
of 17.
tr a n s-(()-Ben zyl 2-(2-a cetyl-3-m eth ylcyclop r op yl)a c-
eta te (9a ): Rf 0.30 (4:1 hexane/ethyl acetate); IR (neat) 1734,
1694, 1498, 1259, 1169 cm-1 1H NMR (CDCl3, 600 MHz) δ
;
1.10 (d, J ) 6.0 Hz, 3H), 1.51 (dd, J ) 4.2, 4.2 Hz, 1H), 1.65
(ddq, J ) 9.6, 6.0, 4.2 Hz, 1H), 1.82 (dddd, J ) 9.6, 8.8, 8.4,
4.2 Hz, 1H), 2.16 (s, 3H), 2.41 (dd, J ) 16.8, 8.4 Hz, 1H), 2.49
(dd, J ) 16.8, 8.8 Hz, 1H), 5.14 (s, 2H), 7.31-7.38 (m, 5H); 13
C
NMR (CDCl3, 150 MHz) δ 12.2, 23.2, 25.6, 30.3, 32.6, 36.4,
66.4, 128.1, 128.2, 128.5, 135.8, 171.9, 207.0; MS m/z (%) 246
(M+, 2), 186 (5), 155 (9), 91 (100). Anal. Calcd for C15H18O3
(246.3): C, 73.15; H, 7.37. Found: C, 73.34; H, 7.20.
cis-(()-Ben zyl 2-(2-a cetyl-3-m eth ylcyclop r op yl)a ceta te
(14a ): Rf 0.46 (4:1 hexane/ethyl acetate); IR (neat) 1736, 1691,
1
1558, 1390, 1166, 740, 698 cm-1; H NMR (CDCl3, 600 MHz)
δ 1.14 (d, J ) 6.4 Hz, 3H), 1.63 (ddq, J ) 8.5, 8.5, 6.4 Hz, 1H),
1.74 (dddd, J ) 8.5, 8.5, 8.2, 6.4 Hz, 1H), 2.11 (dd, J ) 8.5, 8.5
Hz, 1H), 2.22 (s, 3H), 2.77 (dd, J ) 17.6, 8.2 Hz, 1H), 2.84 (dd,
J ) 17.6, 6.4 Hz, 1H), 5.09 and 5.12 (ABq, J ) 9.9 Hz, 2H),
7.30-7.37 (m, 5H); 13C NMR (CDCl3, 150 MHz) δ 6.9, 21.5,
23.0, 27.3, 27.3, 33.3, 66.2, 128.1, 128.1, 128.9, 136.1, 173.1,
207.6; MS m/z (%) 246 (M+, 2), 221 (8), 155 (32), 105 (48), 91
(100), 83 (30); HRMS of 14a , C15H18O3 calcd, 246.1256; found,
246.1259.
F or m a tion of 16 a n d 17 by En olen e Rea r r a n gem en t.
Heating pure 12a or 13a in benzene-d6 at 60 °C for 5 h resulted
in quantitative isomerization to 16 and 17, respectively.
Ben zyl (E)-4-m eth yl-6-oxo-6-p h en yl-2-h exen oa te (16):
Rf 0.60 (4:1 hexane/ethyl acetate); IR 1712, 1687, 1654, 1599,
1581, 1450, cm-1; 1H NMR (C6D6, 600 MHz) δ 0.87 (d, J ) 6.6
Hz, 3H), 2.46 (dd, J ) 17.1, 7.8 Hz, 1H), 2.57 (dd, J ) 17.1,
5.9 Hz, 1H), 2.90 (dddq, J ) 7.8, 7.0, 6.6, 5.9 Hz, 1H), 5.06
and 5.07 (ABq, J AB ) 12.6 Hz, 2H), 5.84 (d, J ) 15.7 Hz, 1H),
7.00 (dd, J ) 15.7, 7.0 Hz, 1H), 7.05-7.27 (m, 8H), 7.68-7.72
(m, 2H); 13C NMR (C6D6, 150 MHz) δ 18.9, 31.9, 44.0, 66.2,
120.1, 128.2, 128.3, 128.6, 128.6, 128.7, 133.0, 136.6, 137.2,
153.5, 166.4, 197.3; MS m/z (%) 308 (M+, 0.1), 290 (3), 262 (18),
174 (12), 105 (100), 91 (76), 82 (63). Anal. Calcd for C20H20O3
(308.4): C, 77.90; H, 6.54. Found: C, 77.92; H, 6.48.
tr a n s-(()-Meth yl 2-(2-ben zoyl-3-m eth ylcyclop r op yl)-
a ceta te (7b): Rf 0.37 (4:1 hexane/ethyl acetate); IR (neat)
2954, 1740, 1662, 1598, 1581, 1450, 1044 cm-1 1H NMR
;
(CDCl3, 600 MHz) δ 1.23 (d, J ) 6.0 Hz, 3H), 1.87 (ddq, J )
9.0, 6.0, 4.2 Hz, 1H), 2.04 (dddd, J ) 9.0, 7.8, 7.2, 4.2 Hz, 1H),
2.26 (dd, J ) 4.2, 4.2 Hz, 1H), 2.48 (dd, J ) 15.6, 7.8 Hz, 1H),
2.55 (dd, J ) 15.6, 7.2 Hz, 1H), 3.68 (s, 3H), 7.45-7.48 (m,
2H), 7.54-7.57 (m, 1H), 7.96-7.98 (m, 2H); 13C NMR (CDCl3,
150 MHz) δ 12.4, 24.4, 26.5, 32.5, 32.6, 51.8, 128.0, 128.5,
132.6, 138.0, 172.6, 199.1; MS m/z (%) 232 (M+, 5), 217 (7),
200 (18), 159 (83), 115 (13), 105 (100). Anal. Calcd for C14H16O3
(232.3): C, 72.39; H, 6.94. Found: C, 72.18; H, 6.94.
cis-(()-Met h yl 2-(2-b en zoyl-3-m et h ylcyclop r op yl)a c-
eta te (12b): Rf 0.42 (4:1 hexane/ethyl acetate); IR (neat) 2953,
1739, 1664, 1597, 1580, 1448, 1213, 724 cm-1; 1H NMR (CDCl3,
600 MHz) δ 1.22 (d, J ) 6.6 Hz, 3H), 1.83 (ddq, J ) 8.4, 8.4,
6.6 Hz, 1H), 1.91 (dddd, J ) 8.4, 8.4, 7.2, 6.6 Hz, 1H), 2.80
(dd, J ) 8.4, 8.4 Hz, 1H), 2.86 (dd, J ) 18.0, 6.6 Hz, 1H), 2.9
(dd, J ) 18.0, 7.2 Hz, 1H), 3.64 (s, 3H), 7.43-7.48 (m, 2H),
7.51-7.54 (m, 1H), 7.92-7.95 (m, 2H); 13C NMR (CDCl3, 150
MHz) δ 7.2, 21.8, 23.0, 24.3, 27.5, 51.5, 127.7, 128.3, 133.1,
139.8, 173.7, 199.5. The titled compound (12b) was found to
be unstable at ambient temperature undergoing an enolene
rearrangement over several days to afford known methyl (E)-
4-methyl-6-oxo-6-phenyl-2-hexenoate, Rf 0.30 (4:1 hexane/ethyl
acetate), which displayed physical and chemical properties
identical with those reported.45
Ben zyl (E)-4-m eth yl-6-oxo-6-[4-(tr iflu or om eth yl)p h en -
yl]-2-h exen oa te (17): Rf 0.45 (4:1 hexane/ethyl acetate); IR
(CHCl3) 1714, 1697, 1655, 1583, 1512, 1456, 1410, 1173, 1066
1
cm-1; H NMR (600 MHz) δ 1.17 (d, J ) 6.8 Hz, 3H), 2.98-
3.18 (m, 3H), 5.17 (s, 2H), 5.91 (d, J ) 15.7 Hz, 1H), 7.02 (dd,
J ) 15.7, 6.8 Hz, 1H), 7.30-7.39 (m, 5H), 7.70-7.78 (m, 2H)
8.01-8.07 (m, 2H); 13C NMR (150 MHz) δ 19.1, 31.8, 42.9, 66.2,
120.1, 123.7 (q, J ) 274 Hz), 125.8 (q, J ) 3.9 Hz), 128.3, 128.3,
128.4, 128.6, 134.5 (q, J ) 33 Hz), 136.0, 152.8, 171.7, 197.0;
MS m/z (%) 376 (M+, 0.1), 270 (8), 242 (11), 173 (62), 145 (28),
91 (100), 82 (83); HRMS of 17, C21H19F3O3 calcd, 376.1286;
found, 376.1274.
tr a n s-(()-Ben zyl 2-{2-m et h yl-3-[4-(t r iflu or om et h yl)-
ben zoyl]cyclop r op yl}a ceta te (8a ): Rf 0.50 (4:1 hexane/ethyl
acetate); mp 91-92 °C (heptane); IR 1726, 1666, 1327, 1173
Gen er a l P r oced u r e for P r ep a r a tion of tr a n s γ-Hy-
d r oxy En on es 21a -d fr om 1a -d . To a mixture of the 1,2-
dioxine (1.2 mmol) in dichloromethane (2 mL) at ambient
temperature was added a mixture of triethylamine (1.2 mmol)
and TPP (0.6 mmol) dissolved in dichloromethane (0.5 mL).
Stirring was continued until cessation of reaction (TLC, ca. 2
h) after which time the volatiles were removed and the residue
subjected to column chromatography to afford the desired trans
γ-hydroxy enone.
1
cm-1; H NMR (CDCl3, 600 MHz) δ 1.23 (d, J ) 6.6 Hz, 3H),
1.92 (ddq, J ) 9.3, 6.6, 4.2 Hz, 1H), 2.08 (dddd, J ) 9.3, 8.4,
6.6, 4.2 Hz, 1H), 2.24 (dd, J ) 4.2, 4.2 Hz, 1H), 2.49 (dd, J )
16.2, 8.4 Hz, 1H), 2.66 (dd, J ) 16.2, 6.6 Hz, 1H), 5.13 and
(44) Avery, T. D.; J ensen, W. P.; Taylor, D. K.; Tiekink, E. R. T Z.
Kristallogr. 1999, 214, 519.
(45) Enders, D.; Frank, U.; Fey, P.; J andeleit, B.; Lohray, B. B. J .
Organomet. Chem. 1996, 519, 147. Methyl (E)-4-methyl-6-oxo-6-phenyl-
2-hexenoate was incorrectly named in this publication.
(E)-4-Hyd r oxy-1,4-d ip h en yl-2-bu ten -1-on e (21a ): yield
82%; Rf 0.50 (2:1 hexane/ethyl acetate); IR (CDCl3) 3419, 1670,
1624, 1599, 1579, 1448 cm-1 1H NMR (CDCl3, 600 MHz) δ
;