The Journal of Organic Chemistry
Note
1
Rf = 0.73 (hexane/EtOAc = 20/1); H NMR (CDCl3, 400 MHz) δ
Methyl 2-(2,2-Difluoro-2-phenylethyl)-4-phenylpent-4-enoate
(6c). 52.8 mg, 32%. Colorless oil; Rf = 0.13 (hexane/EtOAc = 30/
1); H NMR (CDCl3, 400 MHz) δ 7.27−7.41 (m, 10H), δ 5.31 (s,
6.55 (s, 1H), δ 5.93 (s, 1H), δ 3.81 (s, 3H), δ 3.19 (t, J = 18.6 Hz,
2H); 13C{1H} NMR (CDCl3, 100 MHz) δ 166.2, δ 132.3, δ 129.3, δ
121.4−105.5 (m, CF2, CF3), δ 52.4, δ 32.3 (t, J = 21.5 Hz); 19F NMR
(CDCl3, 367 MHz) δ −80.64 (s, 3F), δ −113.4 (s, 2F), δ −121.7 (s,
2F), δ −122.6 (s, 2F), δ −123.0 (s, 2F), δ −126.0 (s, 2F). HRMS
(DART) m/z: [M + H]+ Calcd for C15H7F21O2H 619.0183; Found
619.0160.
1
1H), δ 5.08 (s, 1H), δ 3.52 (s, 3H), δ 2.78−2.89 (m, 2H), δ 2.58−
2.72 (m, 2H), δ 2.20−2.33 (m, 1H); 13C{1H} NMR (CDCl3, 100
MHz) δ 175.0, δ 145.1, δ 139.9, δ 136.6 (t, J = 26.3 Hz), δ 129.8, δ
128.4, δ 128.3, δ 127.7, δ 126.2, δ 124.9 (t, J = 6.2 Hz), δ 122.1 (t, J =
241 Hz), δ 51.7, δ 40.5 (t, J = 27.2 Hz), δ 38.7, δ 38.6; 19F NMR
(CDCl3, 367 MHz) δ −95.0 (s, 2F). IR (neat) 2951 cm−1, 1739 cm−1,
1451 cm−1, 1312 cm−1, 1264 cm−1, 1171 cm−1, 1060 cm−1, 960 cm−1,
4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-Henicosafluoro-
2-methyltridec-1-ene33 (3m). 181.3 mg, 63%. Colorless oil; Rf = 0.90
1
(pentane); H NMR (CDCl3, 400 MHz) δ 5.10 (s, 1H), δ 4.97 (s,
+
906 cm−1, 768 cm−1, 699 cm−1; HRMS (DART) m/z: [M + Na]
1H), δ 2.78 (t, J = 19.2 Hz, 2H), δ 1.88 (s, 3H); 13C{1H} NMR
(CDCl3, 100 MHz) δ 134.2, δ 118.9, δ 121.4−105.0 (m, CF2, CF3), δ
38.7 (t, J = 22.0 Hz), δ 29.7, δ 23.3; 19F NMR (CDCl3, 367 MHz) δ
−80.6 (s, 3F), δ −112.7 (s, 2F), δ −121.6 (s, 10F), δ −122.6 (s, 2F),
δ −123.1 (s, 2F), δ −126.0 (s, 2F).
Calcd for C20H20F2O2Na 353.1325; Found 353.1324.
1-Ethyl 5-Methyl 4-(2,2-Difluoro-2-phenylethyl)-2,2-difluoropen-
tanedioate (7). 143.6 mg, 82%. Colorless oil; Rf = 0.3 (hexane/
EtOAc = 10/1); 1H NMR (CDCl3, 600 MHz) δ 7.47−7.41 (m, 5H),
δ 4.31 (q, J = 7.1 Hz, 2H), δ 3.65 (s, 3H), δ 3.07−3.03 (m, 1H), δ
2.71−2.53 (m, 2H), δ 2.37−2.27 (m, 2H), δ 1.34 (t, J = 7.2 Hz, 3H);
13C{1H} NMR (CDCl3, 150 MHz) δ 173.9, δ 163.4 (t, J = 31.7 Hz),
δ 136.2 (t, J = 25.9 Hz), δ 130.1, δ 128.5, δ 124.8 (t, J = 6.5 Hz), δ
121.7 (t, J = 242.0 Hz), δ 114.9 (t, J = 249.9 Hz), δ 63.1, δ 52.3, δ
41.5 (t, J = 27.3 Hz), δ 36.7 (t, J = 23.0 Hz), δ 33.8 (t, J = 2.9 Hz), δ
13.8; 19F NMR (CDCl3, 565 MHz) δ −95.3 (d, J = 244.1 Hz, 1F), δ
−95.9 (d, J = 244.1 Hz, 1F), δ −105.0 (s, 2F); IR (neat) 2988 cm−1,
2955 cm−1, 1768 cm−1, 1746 cm−1, 1452 cm−1, 1442 cm−1, 1377
cm−1, 1314 cm−1, 1202 cm−1, 1173 cm−1, 1097 cm−1, 954 cm−1, 8522
cm−1, 767 cm−1, 700 cm−1, 662 cm−1; HRMS (DART) m/z: [M +
Na]+ Calcd for C16H18F4O4Na 373.1033; Found 373.1027.
Dimethyl 2-Fluoro-4-methylenepentanedioate (3n). 77.5 mg,
73%. Colorless oil; Rf = 0.40 (hexane/EtOAc = 10/1); H NMR
1
(CDCl3, 400 MHz) δ 6.35 (s, 1H), δ 5.78 (s, 1H), δ 5.10 (ddd, J =
4.0 Hz, 8.8 Hz, 48.8 Hz, 1H), δ 4.26 (q, J = 7.1 Hz, 2H), δ 3.79 (s,
3H), δ 2.77−3.05 (m, 2H), δ 1.31 (t, J = 7.0 Hz, 3H); 13C{1H} NMR
(CDCl3, 100 MHz) δ 169.1 (d, J = 23.8 Hz), δ 166.6, δ 133.8 (d, J =
2.9 Hz), δ 129.4, δ 87.0 (d, J = 87.0), δ 61.6, δ 52.1, δ 35.1 (d, J = 22
Hz), δ 14.1; 19F NMR (CDCl3, 367 MHz) δ −190.9 (s, 1F). IR
(neat) 2986 cm−1, 2956 cm−1, 1761 cm−1, 1724 cm−1, 1634 cm−1,
1442 cm−1, 1335 cm−1, 1309 cm−1, 1277 cm−1, 1211 cm−1, 1153
cm−1, 1090 cm−1, 1044 cm−1, 957 cm−1, 819 cm−1; HRMS (DART)
+
m/z: [M + H] Calcd for C9H13FO4H 205.0871; Found 205.0865.
Ethyl 2-Fluoro-4-phenylpent-4-enoate (3o). 70.8 mg, 60%.
Colorless oil; Rf = 0.43 (hexane/EtOAc = 20/1); 1H NMR
(CDCl3, 400 MHz) δ 5.44 (s, 1H), δ 5.25 (s, 1H), δ 4.95 (ddd, J
= 4.4 Hz, 7.2 Hz, 48 Hz, 1H), δ 4.11−4.23 (m, 2H), δ 2.97−3.23 (m,
2H), δ 1.27 (t, J = 7.0 Hz, 3H); 13C{1H} NMR (CDCl3, 100 MHz) δ
169.4 (d, J = 23.9 Hz), δ 142.1, δ 139.7, δ 128.4, δ 127.8, δ 126.2, δ
116.5, δ 87.3 (d, J = 185 Hz), δ 61.5, δ 38.4 (d, J = 22 Hz), δ 14.0; 19F
NMR (CDCl3, 367 MHz) δ −190.0 (s, 1F). IR (neat) 2983 cm−1,
2939 cm−1, 1760 cm−1, 1740 cm−1, 1496 cm−1, 1445 cm−1, 1373
5-Ethyl 1-Methyl 2-Chloro-4,4-difluoro-2-(2,2,2-trichloroethyl)-
pentanedioate (8). 70.5 mg, 57%. Colorless oil; Rf = 0.3 (hexane/
1
EtOAc = 10/1); H NMR(CDCl3, 400 MHz) δ 4.38−4.33 (q, 2H),
3.86(s, 3H), δ 3.81−3.77 (d, 1H), δ 3.66−3.62 (d, 1H), δ 3.38−3.27
(m, 1H), δ 3.20−3.09 (m, 1H), δ 1.39−1.35 (t, 3H); 13C{1H}
NMR(CDCl3, 100 MHz) δ 168.4, δ 163.2 (t, JF−C = 32.5 Hz), δ 114.0
(t, JF−C = 251.7 Hz), δ 94.0, δ 63.6, δ 63.4, δ 60.8, δ 54.1, δ 42.9 (t,
J
F−C = 48.1 Hz), δ 13.8; 19F NMR (CDCl3, 367 MHz) δ −100.5 (dd,
J = 9.5, 269.0 Hz, 1F), δ −102.9 (dd, J = 9.5, 269.0 Hz, 1F); IR (neat)
1759 cm−1, 1769 cm−1; HRMS (DART) m/z: [M]+ Calcd for
C10H12Cl4F2O4 373.9458; Found 373.9468.
cm−1, 1281 cm−1, 1201 cm−1, 1086 cm−1, 1037 cm−1, 908 cm−1, 779
+
cm−1, 706 cm−1; HRMS (DART) m/z: [M + H]
Calcd for
C13H15FO2Na 245.0947; Found 245.0948.
(E)-N-Isopropyl-N-(2-(phenylsulfonyl)vinyl)propan-2-amine25
(9). 13.4 mg, 10%. Colorless oil; Rf = 0.55 (MeOH); 1H NMR
(CDCl3, 600 MHz) δ 7.83−7.84 (m, 2H), δ 7.43−7.49 (m, 3H), δ
7.39 (d, J = 8 Hz, 1H), δ 4.96 (d, J = 8.8 Hz, 1H), δ 3.59 (s, 2H), δ
1.28−1.00 (m, 12H); 13C{1H} NMR (CDCl3, 150 MHz) δ 145.4, δ
145.2 (d, J = 3.9 Hz), δ 131.3, δ 128.7, δ 126.6, δ 91.2 (t, J = 5.3 Hz),
δ 47.5, δ 23.4, δ 19.4.
1-Ethyl 7-Methyl 2,2-Difluoro-4-hexyl-6-methyleneheptane-
dioate (6a). 80.9 mg, 50%. Colorless oil; Rf = 0.40 (hexane/EtOAc
= 20/1); 1H NMR (CDCl3, 400 MHz) δ 6.22 (s, 1H), δ 5.53 (s, 1H),
δ 4.29 (q, J = 7.2 Hz, 2H), δ 3.74 (s, 3H), δ 2.38 (dd, JH−H = 6.8 Hz,
JH−F = 14.0 Hz, 1H), δ 2.25 (dd, JH−H = 6.8 Hz, JH−F = 14.0 Hz, 1H),
δ 1.9−2.1 (m, 3H), δ 1.2−1.35 (m, 13H), δ 0.86 (t, J = 6.8 Hz, 3H);
13C{1H} NMR (CDCl3, 100 MHz) δ 167.4, δ 164.4 (t, J = 33.0 Hz),
δ 138.6, δ 126.9, δ 116.6 (t, J = 249 Hz), δ 62.7, δ 51.8, δ 37.5 (t, J =
22.0 Hz), δ 37.0, δ 33.7, δ 31.7, δ 31.0, δ 29.3, δ 25.8, δ 22.6, δ 14.0, δ
13.9; 19F NMR (CDCl3, 367 MHz) δ −103.2 (s, 2F); IR (neat) 2930
cm−1, 2858 cm−1, 1769 cm−1, 1724 cm−1, 1631 cm−1, 1441 cm−1,
1375 cm−1, 1332 cm−1, 1305 cm−1, 1197 cm−1, 1154 cm−1, 1083
cm−1, 1021 cm−1, 948 cm−1, 818 cm−1; HRMS (ESI) m/z: [M + Na]
Methyl 2-Methylene-4-((phenylsulfonyl)methyl)decanoate (10).
32.3 mg, 12% (based on 2a in Scheme 3, eq (3)). Colorless oil; Rf =
0.40 (hexane/EtOAc = 20/1); 1H NMR (CDCl3, 400 MHz) δ 7.88−
7.91 (m, 2H), δ 7.54−7.66 (m, 3H), δ 6.19 (s, 1H), δ 5.52 (s, 1H), δ
3.69 (s, 3H), δ 3.04 (dq, J = 6.8 Hz, J = 14.0 Hz, 1H), δ 2.44 (m, 1H),
δ 2.34 (m, 1H), δ 2.15 (m, 1H), δ 1.19−1.70 (m, 13H); 13C{1H}
NMR (CDCl3, 100 MHz) δ 167.0, δ 139.6, δ 137.8, δ 133.4, δ 129.1,
δ 127.9, δ 127.3, δ 58.9, δ 51.8, δ 36.0, δ 33.2, δ 32.2, δ 31.5, δ 29.0, δ
25.7, δ 22.5, δ 14.0; IR (neat) 2927 cm−1, 2857 cm−1, 1767 cm−1,
1724 cm−1, 1631 cm−1, 1446 cm−1, 1307 cm−1, 1147 cm−1, 1087
cm−1, 820 cm−1, 750 cm−1, 689 cm−1, 599 cm−1, 568 cm−1, 533 cm−1;
HRMS (DART) m/z: [M + Na]+ Calcd for C19H28SO4Na 375.1601;
Found 375.1594.
+
Calcd for C17H28F2O4Na 357.1843; Found 357.1848.
Methyl 6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,15,15,15-He-
nicosafluoro-4-hexyl-2-methylenepentadecanoate (6b). 204 mg,
1
56%. Colorless oil; Rf = 0.33 (hexane/EtOAc = 20/1); H NMR
(CDCl3, 400 MHz) δ 6.25 (s, 1H), δ 5.55 (s, 1H), δ 3.76 (s, 3H), δ
2.45 (dd, JH−H = 7.2 Hz, JH−F = 16.0 Hz, 1H), δ 2.30 (dd, JH−H = 7.2
Hz, JH−F = 16.0 Hz, 1H), δ 1.95−2.14 (m, 3H), δ 1.27−1.39 (m,
10H), δ 0.88 (t, J = 6.6 Hz, 3H); 13C{1H} NMR (CDCl3, 100 MHz)
δ 167.4, δ 138.5, δ 132.2, δ 126.9, δ 107.8−121.5 (m, CF2, CF3), δ
95.4, δ 51.8, δ 37.3, δ 34.1, δ 33.5 (t, J = 21.0 Hz), δ 31.7, δ 31.6, δ
30.3, δ 29.3, δ 26.0, δ 22.6, δ 14.0, δ 13.9; 19F NMR (CDCl3, 367
MHz) δ −80.7 (s, 3F), δ −112.6 (s, 2F), δ −121.5 (s, 2F), δ −121.7
(s, 2F), δ −122.6 (s, 2F), δ −123.5 (s, 2F), δ −126.0 (s, 2F); IR
(neat) 2932 cm−1, 2861 cm−1, 1730 cm−1, 1632 cm−1, 1441 cm−1,
1336 cm−1, 1244 cm−1, 1109 cm−1, 949 cm−1, 817 cm−1, 644 cm−1,
556 cm−1; HRMS (DART) m/z: [M + NH4]+ Calcd for
C23H23F21O2NH4 748.1701; Found 748.1697.
ASSOCIATED CONTENT
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* Supporting Information
The Supporting Information is available free of charge on the
Detailed information on light sources, photoirradiation
conditions, and copies of NMR spectra (PDF)
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J. Org. Chem. XXXX, XXX, XXX−XXX