The Journal of Organic Chemistry
Note
Benzyl (E)-4-Methyl-2-methylene-3-styrylpent-3-enoate (3fa).
Yield: 33.3 mg (35%); pale yellow oil; Rf = 0.2 (PE:EA = 20:1);
1H NMR (400 MHz, CDCl3) δ 7.36−7.26 (m, 10H), 7.20−7.16 (m,
NMR (100 MHz, CDCl3) δ 167.2, 166.4, 150.8, 140.0, 138.9, 138.6,
130.4, 130.1, 128.1, 126.4, 125.4 (q, J = 3.8 Hz), 117.7, 65.5, 37.0,
35.7, 33.8, 30.7, 28.4, 28.3, 26.5; HRMS (ESI, m/z): calcd for
C23H27F3NO3 [M + H]+ 422.1943, found 422.1927; IR (film): 1131,
1327, 1394, 1647, 1724, 2934 cm−1.
Ethyl (E)-3-cyclohexylidene-6-(dimethylamino)-2-methylene-6-
oxohex-4-enoate (3ii). Yield: 103.8 mg (71%); pale yellow oil; Rf
= 0.3 (PE:EA = 1:1); 1H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 15.0
Hz, 1H), 6.50 (d, J = 1.5 Hz, 1H), 6.03 (d, J = 15.0 Hz, 1H), 5.50 (d,
J = 1.6 Hz, 1H), 4.18 (q, J = 7.1 Hz, 2H), 3.00 (s, 6H), 2.54−2.52 (m,
2H), 2.20−2.17 (m, 2H), 1.66−1.55 (m, 6H), 1.25 (t, J = 7.1 Hz,
3H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.5, 166.8, 150.4, 139.2,
139.1, 129.0, 126.7, 117.6, 60.9, 37.2, 35.8, 33.8, 30.6, 28.3, 28.2, 26.6,
14.2; HRMS (ESI, m/z): calcd for C17H26NO3 [M + H]+ 292.1913,
found 292.1906; IR (film): 1194, 1249, 1393, 1596, 1646, 1718, 2850,
2932 cm−1.
1H), 6.61 (d, J = 1.9 Hz, 1H), 6.22 (d, J = 16.0 Hz, 1H), 5.59 (d, J =
1.9 Hz, 1H), 5.20 (s, 2H), 2.00 (s, 3H), 1.76 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3) δ 166.7, 139.4, 138.0, 136.3, 135.5, 130.6, 129.9,
128.8, 128.5, 128.5, 128.0, 127.8, 127.1, 126.8, 126.4, 66.4, 23.3, 20.2;
HRMS (ESI, m/z): calcd for C22H23O2 [M + H]+ 319.1698, found
319.1692; IR (film): 1173, 1256, 1307, 1720, 2916, 3029 cm−1.
Benzyl (E)-6-(Dimethylamino)-2-methylene-6-oxo-3-(propan-2-
ylidene)hex-4-enoate (3ga). Yield: 62.8 mg (67%); colorless oil; Rf
= 0.5 (PE:EA = 1:1); 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 15.0
Hz, 1H), 7.35−7.29 (m, 5H), 6.56 (d, J = 1.8 Hz, 1H), 5.92 (d, J =
15.0 Hz, 1H), 5.54 (d, J = 1.8 Hz, 1H), 5.18 (s, 2H), 2.97 (s, 3H),
2.84 (s, 3H), 2.03 (s, 3H), 1.77 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ 167.3, 166.4, 142.5, 139.5, 139.1, 136.1, 130.0, 129.7, 128.5,
128.1, 128.0, 117.3, 66.5, 37.1, 35.7, 23.5, 20.4; HRMS (ESI, m/z):
calcd for C19H24NO3 [M + H]+ 314.1756, found 314.1751; IR (film):
1126, 1179, 1255, 1392, 1597, 1647, 1720 cm−1.
6-Benzyl 1-Ethyl (2E,4E)-4-ethylidene-5-methylenehex-2-ene-
dioate (3ja). Yield: 71.9 mg (80%), colorless oil, Rf = 0.3 (PE:EA
1
= 20:1); H NMR (400 MHz, CDCl3) δ 7.74 (d, J = 15.8 Hz, 1H),
Ethyl (E)-6-(Dimethylamino)-2-methylene-6-oxo-3-(propan-2-
ylidene)hex-4-enoate (3gi). Yield: 67.1 mg (54%); pale yellow oil;
Rf = 0.2 (PE:EA = 1:1); 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J =
15.0 Hz, 1H), 6.53 (d, J = 1.8 Hz, 1H), 5.99 (d, J = 15.0 Hz, 1H),
5.52 (d, J = 1.8 Hz, 1H), 4.19 (q, J = 7.1 Hz, 2H), 3.00 (s, 6H), 2.03
(s, 3H), 1.78 (s, 3H), 1.25 (t, J = 7.1 Hz, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ 167.4, 166.6, 142.3, 139.6, 139.3, 129.8, 129.4, 117.1,
60.9, 37.2, 35.8, 23.5, 20.4, 14.2; HRMS (ESI, m/z): calcd for
C14H22NO3 [M + H]+ 252.1600, found 252.1593; IR (film): 1189,
1255, 1393, 1596, 1647, 1718, 2923 cm−1.
Benzyl (E)-3-(3-(Dimethylamino)-3-oxoprop-1-en-1-yl)-4-ethyl-
2-methylenehex-3-enoate (3ha). Yield: 64.6 mg (63%); pale yellow
oil; Rf = 0.5 (PE:EA = 1:1); 1H NMR (400 MHz, CDCl3) δ 7.77 (d, J
= 15.0 Hz, 1H), 7.32−7.28 (m, 5H), 6.55 (d, J = 1.8 Hz, 1H), 5.95 (d,
J = 15.0 Hz, 1H), 5.55 (d, J = 1.8 Hz, 1H), 5.17 (s, 2H), 2.97 (s, 3H),
2.85 (s, 3H), 2.41 (q, J = 7.5 Hz, 2H), 2.09 (q, J = 7.5 Hz, 2H), 1.07
(t, J = 7.5 Hz, 3H), 0.93 (t, J = 7.5 Hz, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ 167.3, 166.6, 153.6, 139.4, 138.8, 136.0, 129.7, 128.9,
128.5, 128.1, 127.9, 117.8, 66.5, 37.1, 35.7, 27.5, 24.0, 14.0, 12.8;
HRMS (ESI, m/z): calcd for C21H28NO3 [M + H]+ 342.2069, found
342.2064; IR (film): 1175, 1392, 1599, 1646, 1719, 2922, 2968 cm−1.
Benzyl (E)-3-Cyclohexylidene-6-(dimethylamino)-2-methylene-
6-oxohex-4-enoate (3ia). Yield: 79.9 mg (75%); yellow oil; Rf =
0.3 (PE:EA = 1:1); 1H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 15.0
Hz, 1H), 7.33−7.30 (m, 5H), 6.54 (d, J = 1.8 Hz, 1H), 5.96 (d, J =
15.0 Hz, 1H), 5.53 (d, J = 1.8 Hz, 1H), 5.18 (s, 2H), 2.97 (s, 3H),
2.85 (s, 3H), 2.54−2.51 (m, 2H), 2.19−2.16 (m, 2H), 1.62−1.55 (m,
4H), 1.51−1.47 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ
167.4, 166.6, 150.7, 139.0, 138.3, 136.0, 129.6, 128.5, 128.1, 128.0,
126.6, 117.8, 66.5, 37.1, 35.8, 33.8, 30.7, 28.3, 28.2, 26.6; HRMS (ESI,
m/z): calcd for C22H28NO3 [M + H]+ 354.2069, found 354.2064; IR
(film): 1136, 1393, 1597, 1646, 1720, 2851, 2928 cm−1.
[1,1′-Biphenyl]-4-ylmethyl (E)-3-Cyclohexylidene-6-(dimethyla-
mino)-2-methylene-6-oxohex-4-enoate (3ib). Yield: 87.2 mg
(68%); pale yellow oil; Rf = 0.5 (PE:EA = 1:1); 1H NMR (400
MHz, CDCl3) δ 7.89 (d, J = 15.0 Hz, 1H), 7.58−7.54 (m, 4H), 7.46−
7.35 (m, 5H), 6.56 (d, J = 1.7 Hz, 1H), 5.96 (d, J = 15.0 Hz, 1H),
5.54 (d, J = 1.7 Hz, 1H), 5.22 (s, 2H), 2.93 (s, 3H), 2.82 (s, 3H),
2.55−2.52 (m, 2H), 2.20−2.17 (m, 2H), 1.65−1.50 (m, 6H);
13C{1H} NMR (100 MHz, CDCl3) δ 167.4, 166.6, 150.7, 141.0,
140.6, 139.0, 138.9, 135.0, 129.7, 128.9, 128.6, 127.5, 127.2, 127.1,
126.6, 117.8, 66.3, 37.1, 35.7, 33.9, 30.7, 28.4, 28.2, 26.6; HRMS (ESI,
m/z): calcd for C28H32NO3 [M + H]+ 430.2382, found 430.2376; IR
(film): 1139, 1187, 1646, 1719, 2852, 2898, 2929 cm−1.
4-(Trifluoromethyl)benzyl (E)-3-Cyclohexylidene-6-(dimethyla-
mino)-2-methylene-6-oxohex-4-enoate (3ie). Yield: 93.3 mg
(74%); pale yellow oil; Rf = 0.4 (PE:EA = 1:1); 1H NMR (400
MHz, CDCl3) δ 7.90 (d, J = 15.0 Hz, 1H), 7.61−7.56 (m, 2H), 7.46−
7.41 (m, 2H), 6.57 (d, J = 1.7 Hz, 1H), 5.94 (d, J = 15.0 Hz, 1H),
5.57 (d, J = 1.7 Hz, 1H), 5.23 (s, 2H), 2.98 (s, 3H), 2.83 (s, 3H),
2.59−2.49 (m, 2H), 2.29−2.14 (m, 2H), 1.56 (m, 6H); 13C{1H}
7.35−7.32 (m, 8H), 6.63 (d, J = 1.6 Hz, 0.42H), 6.36 (d, J = 1.7 Hz,
1H), 6.18 (q, J = 7.2 Hz, 0.46H), 5.94 (q, J = 7.3 Hz, 1H), 5.68 (d, J =
15.8 Hz, 1H), 5.67 (d, J = 1.7 Hz, 1H), 5.60 (d, J = 15.9 Hz, 0.56H),
5.19 (s, 1H), 5.18 (s, 2H), 4.21−4.15 (m, 3H), 1.95 (d, J = 7.2 Hz,
3H), 1.72 (d, J = 7.1 Hz, 1.39H), 1.30−1.25 (m, 4.7H); 13C{1H}
NMR (100 MHz, CDCl3) δ 167.2, 167.1, 166.1, 165.4, 146.9, 144.6,
140.9, 139.1, 138.4, 136.4, 136.3, 135.9, 135.8, 135.1, 131.0, 129.1,
128.6, 128.5, 128.2, 128.1, 127.9, 120.3, 117.8, 114.3, 66.8, 66.7, 60.4,
60.3, 20.7, 20.4, 14.3, 14.3; HRMS (ESI, m/z): calcd for C18H21O4
[M + H]+ 301.1440, found 301.1434; IR (film): 760, 1176, 1272,
1714, 2959 cm−1.
6-(((3r,5r,7r)-Adamantan-1-yl)methyl) 1-Ethyl (E)-4-cyclohexyli-
dene-5-methylenehex-2-enedioate (3ik). Yield: 84.5 mg (69%);
1
yellow oil; Rf = 0.4 (PE:EA = 1:1); H NMR (400 MHz, CDCl3) δ
7.89 (d, J = 15.0 Hz, 1H), 6.51 (d, J = 2.0 Hz, 1H), 6.03 (d, J = 15.0
Hz, 1H), 5.49 (d, J = 2.0 Hz, 1H), 3.71 (s, 2H), 2.99 (s, 6H), 2.55−
2.53 (m, 2H), 2.22−2.19 (m, 2H), 1.95−1.91 (m, 3H), 1.72−1.54
(m, 12H), 1.48 (d, J = 2.1 Hz, 6H); 13C{1H} NMR (100 MHz,
CDCl3) δ 167.4, 167.0, 150.2, 139.2, 139.1, 129.0, 126.9, 117.7, 74.4,
39.2, 37.2, 36.9, 35.8, 33.9, 33.4, 30.6, 28.4, 28.2, 28.0, 26.6; HRMS
(ESI, m/z): calcd for C26H38NO3 [M + H]+ 412.2852, found
412.2851; IR (film): 1248, 1393, 1597, 1648, 1718, 2850, 2908 cm−1.
Naphthalen-1-ylmethyl (E)-3-Cyclohexylidene-6-(dimethylami-
no)-2-methylene-6-oxohex-4-enoate (3im). Yield: 79.1 mg (65%);
pale yellow oil; Rf = 0.4 (PE:EA = 1:1); 1H NMR (400 MHz, CDCl3)
δ 7.99−7.96 (m, 1H), 7.87−7.81 (m, 3H), 7.54−7.49 (m, 3H), 7.42
(dd, J = 8.2, 7.1 Hz, 1H), 6.51 (d, J = 1.8 Hz, 1H), 5.90 (d, J = 15.0
Hz, 1H), 5.63 (s, 2H), 5.50 (d, J = 1.8 Hz, 1H), 2.93 (s, 3H), 2.67 (s,
3H), 2.50−2.47 (m, 2H), 2.11−2.09 (m, 2H), 1.57−1.48 (m, 4H),
1.41−1.36 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 167.3,
166.6, 150.6, 139.0, 138.9, 133.7, 131.5, 131.5, 129.6, 129.2, 128.6,
127.4, 126.6, 126.5, 125.9, 125.2, 123.7, 117.7, 65.0, 36.9, 35.7, 33.8,
30.6, 28.2, 28.1, 26.6; HRMS (ESI, m/z): calcd for C26H30NO3 [M +
H]+ 404.2226, found 404.2218; IR (film): 1188, 1392, 1598, 1645,
1719, 2855, 2926 cm−1.
Ethyl (4E)-3-cyclohexylidene-6-(dimethylamino)-2-ethylidene-6-
oxohex-4-enoate (3in). Yield: 33.3 mg (36%); pale yellow oil; Rf =
0.4 (PE:EA = 1:1); 1H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 14.9
Hz, 0.46H), 7.82 (d, J = 14.9 Hz, 1H), 7.12 (q, J = 7.0 Hz, 0.46H),
6.11 (d, J = 14.9 Hz, 1H), 5.97 (d, J = 14.9 Hz, 0.46H), 5.89 (q, J =
7.2 Hz, 1H), 4.17−4.11 (m, 2.9H), 3.02−2.99 (m, 8.8 H), 2.94−2.92
(m, 0.9H), 2.60−2.55 (m, 0.9H), 2.51−2.48 (m, 2H), 2.24−2.21 (m,
2H), 2.10 (d, J = 7.2 Hz, 3H), 1.64 (d, J = 7.0 Hz, 1.4H), 1.61−1.56
(m, 8.8H), 1.22 (td, J = 7.2, 1.5 Hz, 4.4H); 13C{1H} NMR (100
MHz, CDCl3) δ 167.7, 167.7, 167.4, 167.1, 150.8, 150.3, 140.6, 140.3,
139.6, 138.2, 132.2, 131.6, 128.6, 124.1, 117.7, 116.8, 60.5, 60.2, 37.4,
37.3, 35.8, 35.7, 33.7, 33.6, 30.7, 30.5, 28.4, 28.3, 28.0, 26.7, 15.6,
15.1, 14.3, 14.2; HRMS (ESI, m/z): calcd for C18H28NO3 [M + H]+
306.2069, found 306.2068; IR (film): 1192, 1391, 1595, 1645, 1713,
2853, 2933 cm−1.
5377
J. Org. Chem. 2021, 86, 5371−5379