The Journal of Organic Chemistry
Article
Hz, 1H), 1.93 (dd, J = 6.9, 1.7 Hz, 3H), 1.83 (d, J = 2.5 Hz, 3H), 1.32
(d, J = 7.1 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 196.6, 144.0,
128.5, 79.8, 77.6, 37.7, 18.5, 17.2, 3.9; HRMS (ESI) 159.0781,
[C9H12ONa]+ requires 159.0780. The (alkynylmethyl) vinyl ketone
(84 mg) with NEt3 (85 μL) for 2 h provided AVK 14a (15 mg, 18%)
7.31−7.28 (m, 2H), 7.26−7.25 (m, 1H), 6.87 (dq, J = 15.2, 6.8 Hz,
1H), 6.62 (dd, J = 15.2, 1.5 Hz, 1H), 6.57 (s, 1H), 1.80 (dd, J = 6.9,
1.4 Hz, 3H), 1.27 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 213.3,
189.1, 142.1, 133.0, 129.5 129.2, 127.9, 127.1, 121.8, 99.4, 34.9, 29.8,
18.3; HRMS (ESI) 263.1397, [C17H20ONa]+ requires 263.1406.
(E)-5-tert-Butyl-8,8-dimethylnon-2-en-6-yn-4-one and (E)-5-tert-
Butyl-8,8-dimethylnona-2,6,7-trien-4-one (14f). Enynol 12f (114
mg) with DMP (328 mg) and NaHCO3 (420 mg), then
chromatography (10% Et2O/pentane) afforded the (alkynylmethyl)
vinyl ketone (42 mg, 37%) as an oil: IR (film) 2242, 1692, 1625 cm−1;
1H NMR (500 MHz, CDCl3) δ 6.90 (dq, J = 15.4, 6.9 Hz, 1H), 6.55
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as an oil: IR (film) 1950, 1667, 1629 cm−1; H NMR (500 MHz,
CDCl3) δ 6.89 (dq, J = 14.9, 7.3 Hz, 1H), 6.72 (dd, J = 15.3, 1.5 Hz,
1H), 5.54−5.49 (m, J = 2.3 Hz, 1H), 1.88 (dd, J = 6.8, 1.4 Hz, 3H),
1.83−1.81 (m, 6H); 13C NMR (125 MHz, CDCl3) δ 212.7, 190.5,
141.3, 127.0, 104.4, 89.3, 18.2, 13.9, 13.6; HRMS (ESI) 159.0773,
[C9H12ONa]+ requires 159.0780.
(dq, J = 15.4, 1.6 Hz, 1H), 3.09 (s, 1H), 1.90 (dd, J = 6.9, 1.7 Hz, 3H),
1.24 (s, 9H), 1.03 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 196.9,
142.5, 129.8, 95.2, 75.5, 55.4, 34.9, 31.2, 28.1, 27.8, 18.4; HRMS (ESI)
243.1719, [C15H24ONa]+ requires 243.1719. The (alkynylmethyl)
vinyl ketone (34 mg) with NEt3 (0.5 mL) for 15 h yielded AVK 14f
(E)-3-Methyl-1-phenylhept-5-en-1-yn-4-one and (E)-3-Methyl-1-
phenylhepta-1,2,5-trien-4-one (14b). Enynol 12b (104 mg) with
DMP (304 mg) and NaHCO3 (488 mg), then chromatography (20%
Et2O/pentane) gave 36 mg (35%) of an oil that was an inseparable
mixture of the (alkynylmethyl) vinyl ketone and 14b in a 1.5:1 ratio
1
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(20 mg, 59%) as an oil: IR (film) 1942, 1675, 1633 cm−1; H NMR
(respectively) by H NMR. NMR data for the (alkynylmethyl) vinyl
1
ketone: H NMR (500 MHz, CDCl3) δ 7.43−7.40 (m, 2H), 7.39−
(500 MHz, CDCl3) δ 6.81 (dq, J = 15.2, 6.5 Hz, 1H), 6.73 (dq, J =
15.2, 1.3 Hz, 1H), 5.55 (s, 1H), 1.85 (dd, J = 6.5, 1.3 Hz, 3H), 1.19 (s,
9H), 1.13 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 209.2, 189.8,
140.5, 129.0, 120.0, 107.1, 33.4, 33.2, 30.1, 29.7, 18.2; HRMS (ESI)
243.1708, [C15H24ONa]+ requires 243.1719.
7.34 (m, 1H), 7.32−7.28 (m, 2H), 7.07 (dq, J = 15.5, 6.9 Hz, 1H),
6.57−6.53 (m, 1H), 3.67 (q, J = 7.0 Hz, 1H), 1.94 (dd, J = 6.9, 1.7 Hz,
3H), 1.43 (d, J = 7.1 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 195.7,
144.5, 131.8, 129.1, 128.4, 128.4, 128.3, 88.1, 84.1, 38.3, 18.6, 16.9.
The 1.5:1 mixture of the (alkynylmethyl) vinyl ketone and 14b (25
mg) with NEt3 (0.10 mL) for 1 h afforded homogeneous AVK 14b
(E)-4,8-Dimethylnon-6-en-2-yn-5-one and (E)-4,8-Dimethylnona-
2,3,6-trien-5-one (14g). Enynol 12g (105 mg) with DMP (414 mg)
and NaHCO3 (501 mg), then chromatography (20% Et2O/pentane)
yielded the (alkynylmethyl) vinyl ketone (94 mg, 91%) as an oil: IR
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(25 mg, 99%) as an oil: IR (film) 1938, 1717, 1671, 1629 cm−1; H
NMR (500 MHz, CDCl3) δ 7.39−7.36 (m, 2H), 7.33−7.29 (m, 3H),
6.96 (dq, J = 15.2, 6.9 Hz, 1H), 6.72 (dq, J = 15.2, 1.6 Hz, 1H), 6.57
(q, J = 2.7 Hz, 1H), 1.98 (d, J = 2.8 Hz, 3H), 1.84 (dd, J = 6.9, 1.6 Hz,
3H); 13C NMR (125 MHz, CDCl3) δ 214.7, 189.6, 142.8, 132.8,
129.5, 128.3, 127.7, 127.4, 108.8, 98.4, 18.6, 14.1; HRMS (ESI)
221.0931, [C14H14ONa]+ requires 221.0937.
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(film) 2350, 1704, 1633 cm−1; H NMR (500 MHz, CDCl3) δ 6.95
(dd, J = 15.7, 6.7 Hz, 1H), 6.37 (d, J = 15.7 Hz, 1H), 3.45−3.41 (m,
1H), 2.49 (octet, J = 6.8 Hz, 1H), 1.83 (d, J = 1.7 Hz, 3H), 1.32 (d, J =
7.1 Hz, 3H), 1.09 (d, J = 6.8 Hz, 6H); 13C NMR (125 MHz, CDCl3) δ
197.2, 154.9, 124.1, 79.7, 77.7, 37.7, 31.4, 21.4, 17.2, 3.8; HRMS (ESI)
187.1090, [C11H16ONa]+ requires 187.1093. The (alkynylmethyl)
vinyl ketone (81 mg) with NEt3 (69 μL) for 24 h gave AVK 14g (44
(E)-5-tert-Butyloct-2-en-6-yn-4-one and (E)-5-tert-Butylocta-
2,5,6-trien-4-one (14c). Enynol 12c (103 mg) with DMP (414 mg)
and NaHCO3 (633 mg), then chromatography (10% Et2O/pentane)
provided the (alkynylmethyl) vinyl ketone (73 mg, 72%) as an oil: IR
1
mg, 54%) as an oil: IR (film) 1950, 1671, 1625 cm−1; H NMR (500
MHz, CDCl3) δ 6.84 (dd, J = 15.5, 6.9 Hz, 1H), 6.65 (d, J = 15.5 Hz,
1H), 5.54−5.48 (m, 1H), 2.45 (octet, J = 6.8 Hz, 1H), 1.83−1.81 (m,
6H), 1.06 (d, J = 6.8 Hz, 6H); 13C NMR (125 MHz, CDCl3) δ 212.7,
191.0, 152.4, 122.7, 104.6, 89.3, 31.2, 21.6, 14.0, 13.6; HRMS (ESI)
187.1085, [C11H16ONa]+ requires 187.1093.
(E)-3,7-Dimethyl-1-phenyloct-5-en-1-yn-4-one and (E)-3,7-Di-
methyl-1-phenylocta-1,2,5-trien-4-one (14h). Enynol 12h (116
mg) with DMP (298 mg) and NaHCO3 (420 mg), then
chromatography (10% Et2O/pentane) provided the (alkynylmethyl)
vinyl ketone (87 mg, 76%) as an oil: IR (film) 2312, 1700, 1638 cm−1;
1H NMR (500 MHz, CDCl3) δ 7.42−7.40 (m, 2H), 7.31−7.29 (m,
3H), 7.03 (dd, J = 15.7, 6.7 Hz, 1H), 6.47 (dd, J = 15.7, 1.3 Hz, 1H),
3.69 (q, J = 7.0 Hz, 1H), 2.51 (octet of doublets, J = 6.8, 1.3 Hz, 1H),
1.45 (d, J = 7.0 Hz, 3H), 1.10 (d, J = 6.8 Hz, 6H); 13C NMR (125
MHz, CDCl3) δ 196.3, 155.4, 131.7, 128.4, 128.2, 124.1, 123.3, 88.2,
84.1, 38.3, 31.4, 21.4, 16.9; HRMS (ESI) 249.1246, [C16H18ONa]+
requires 249.1250. The (alkynylmethyl) vinyl ketone (74 mg) with
NEt3 (0.5 mL) for 1 h gave AVK 14h (74 mg, 99%) as an oil: IR (film)
1938, 1708, 1675, 1629 cm−1; 1H NMR (500 MHz, CDCl3) δ 7.36 (t,
J = 7.5 Hz, 2H), 7.31−7.26 (m, 3H), 6.88 (dd, J = 15.4, 7.1 Hz, 1H),
6.63 (d, J = 15.4 Hz, 1H), 6.56 (q, J = 2.7 Hz, 1H), 2.40 (octet, J = 6.8
Hz, 1H), 1.97 (d, J = 2.7 Hz, 3H), 1.00 (d, J = 6.7 Hz, 3H), 0.99 (d, J
= 6.6 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 214.4, 189.9, 153.5,
132.5, 129.1, 127.9, 127.3, 122.9, 108.5, 98.0, 31.3, 21.6 (2C), 13.9;
HRMS (ESI) 249.1246, [C16H18ONa]+ requires 249.1250.
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(film) 2238, 1692, 1629 cm−1; H NMR (500 MHz, CDCl3) δ 6.91
(dq, J = 15.0, 7.3 Hz, 1H), 6.49 (dq, J = 15.4, 1.6 Hz, 1H), 3.17 (q, J =
2.4 Hz, 1H), 1.91 (dd, J = 6.9, 1.5 Hz, 3H), 1.87 (d, J = 2.5 Hz, 3H),
1.03 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 196.9, 143.0, 130.2,
81.5, 75.9, 55.1, 35.0, 28.1, 18.4, 3.9; HRMS (ESI) 201.1242,
[C12H18ONa]+ requires 201.1250. The (alkynylmethyl) vinyl ketone
(65 mg) with NEt3 (0.5 mL) for 12 h gave AVK 14c (15 mg, 18%) as
an oil: IR (film) 1941, 1675, 1629 cm−1; 1H NMR (500 MHz, CDCl3)
δ 6.81 (dq, J = 15.2, 6.9 Hz, 1H), 6.65 (d, J = 15.3 Hz, 1H), 5.52 (q, J
= 7.2 Hz, 1H), 1.86 (d, J = 7.0 Hz, 3H), 1.81 (d, J = 7.2 Hz, 3H), 1.18
(s, 9H); 13C NMR (125 MHz, CDCl3) δ 212.0, 190.4, 140.9, 129.5,
117.8, 90.7, 33.7, 29.7, 18.3, 13.9; HRMS 201.1241, [C12H18ONa]+
requires 201.1250.
(E)-5,8,8-Trimethylnona-2,5,6-trien-4-one (14d). Trienol 13d (141
mg) with DMP (489 mg) and NaHCO3 (648 mg), then
chromatography (5% Et2O/pentane) yielded AVK 14d (58 mg,
42%) as an oil: IR (film) 1950, 1675, 1629 cm−1; 1H NMR (500 MHz,
CDCl3) δ 6.89 (dq, J = 15.2, 6.8 Hz, 1H), 6.76 (dq, J = 15.3, 1.5 Hz,
1H), 5.54 (q, J = 2.7 Hz, 1H), 1.87 (dd, J = 6.8, 1.5 Hz, 3H), 1.85 (d, J
= 2.7 Hz, 3H), 1.13 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 210.1,
194.7, 141.3, 126.9, 106.9, 106.1, 33.5, 30.3, 18.3, 14.1; HRMS (ESI)
201.1241, [C12H18ONa]+ requires 201.1250.
(E)-3-tert-Butyl-1-phenylhept-5-en-1-yn-4-one and (E)-3-tert-
Butyl-1-phenylhepta-1,2,5-trien-4-one (14e). Enynol 12e (134 mg)
with DMP (395 mg) and NaHCO3 (503 mg), then chromatography
(10% Et2O/pentane) yielded the (alkynylmethyl) vinyl ketone (90
(E)-4-tert-Butyl-8-methylnon-6-en-2-yn-5-one and (E)-4-tert-
Butyl-8-methylnona-2,3,6-trien-5-one (14i). Enynol 12i (64 mg)
with DMP (168 mg) and NaHCO3 (255 mg), then chromatography
(10% Et2O/pentane) provided the (alkynylmethyl) vinyl ketone (48
1
mg, 69%) as an oil: IR (film) 2317, 1692, 1629 cm−1; H NMR (500
MHz, CDCl3) δ 7.45−7.43 (m, 2H), 7.31−7.30 (m, 3H), 6.97 (dq, J =
15.4, 6.9 Hz, 1H), 6.59 (dd, J = 15.4, 1.6 Hz, 1H), 3.40 (s, 1H), 1.91
(dd, J = 6.9, 1.6 Hz, 3H), 1.12 (s, 9H); 13C NMR (125 MHz, CDCl3)
δ 195.9, 143.5, 131.8, 129.9, 128.4, 128.2, 123.5, 86.7, 86.3, 55.9, 35.5,
28.3, 18.5; HRMS (ESI) 263.1409, [C17H20ONa]+ requires 263.1406.
The (alkynylmethyl) vinyl ketone (78 mg) with NEt3 (50 μL) for 4 h
provided AVK 14e (77 mg, 99%) as an oil: IR (film) 1925, 1714, 1671,
1
mg, 76%) as an oil: IR (film) 2317, 1692, 1629 cm−1; H NMR (500
MHz, CDCl3) δ 6.85 (dd, J = 15.6, 6.8 Hz, 1H), 6.39 (dd, J = 15.6, 1.4
Hz, 1H), 3.20 (q, J = 2.5 Hz, 1H), 2.47 (octet of doublets, J = 6.8, 1.4
Hz, 1H), 1.86 (d, J = 2.5 Hz, 3H), 1.07 (d, J = 6.8 Hz, 3H), 1.07 (d, J
= 6.8 Hz, 3H), 1.03 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 197.5,
153.8, 126.1, 81.4, 75.9, 55.1, 35.0, 31.3, 28.1, 21.5 (2C), 3.9; HRMS
(ESI) 229.1553, [C14H22ONa]+ requires 229.1563. The (alkynylmeth-
1
1625 cm−1; H NMR (500 MHz, CDCl3) δ 7.36 (t, J = 7.5 Hz, 2H),
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J. Org. Chem. 2015, 80, 1042−1051