The Journal of Organic Chemistry
Note
1
4
19
2
-Fluoro-1-phenylethanone (2a): Isolated yield (Table 1,
(d, J = 8 Hz, 2H); F NMR (376 Hz, CDCl ) δ −146.52 (d, J = 50
3
1
13
entry 5), 0.0635 g (64%); H NMR (300 MHz, CDCl ) δ 5.54 (d, J =
Hz); C NMR (100 MHz, CDCl ) δ 93.87, 96.43, 128.91, 129.63,
129.66, 131.12, 134.74, 187.20, 187.42.
3
3
19
4
−
1
7 Hz, 2H), 7.48−7.91 (m, 5H); F NMR (283 MHz, CDCl ) δ
3
231.84 (t, J = 47 Hz); 13C NMR (75 MHz, CDCl ) δ 83.5 (d, J =
3
81 Hz), 127.8 (d, J = 2.5 Hz), 128.9, 133.7, 134.1, 193.4 (d, J = 15.5
Hz).
-Fluoro-1-(2-naphthyl)ethanone (2b): Isolated yield (Table
ASSOCIATED CONTENT
Supporting Information
H, F, and C NMR spectra of products 2a−2k. This
■
*
S
1
5
2
1
19
13
1
2
4
, entry 3), 0.120 g (64%); H NMR (300 MHz, CDCl ) δ 5.66 (d, J =
3
19
7 Hz, 2H), 7.56−7.67 (m, 2H), 7.88−7.98 (m, 4H), 8.41 (s, 1H);
F
13
NMR (283 MHz, CDCl ) δ −230.98 (t, J = 47 Hz, 1F); C NMR (75
3
MHz, CDCl ) δ 83.6 (d, J = 181 Hz), 123.1 (d, J = 1.9 Hz), 127.1,
3
AUTHOR INFORMATION
Corresponding Author
1
1
27.84, 128.86, 129.0, 129.6, 129.8 (d, J = 3.2 Hz), 131.0, 132.3, 135.9,
93.3 (d, J = 15.5 Hz).
-Fluoro-1-(1-naphthyl)ethanone (2c):.
■
*
1
0,14
2
Isolated yield
1
(
Table 2, entry 6), 0.130 g (69%); H NMR (300 MHz, CDCl ) δ
3
Notes
5
.52 (d, J = 47 Hz, 2H), 7.50−8.08 (m, 6H), 8.70 (d, J = 8.4 Hz, 1H);
1
9
13
The authors declare no competing financial interest.
F NMR (283 MHz, CDCl ) δ −226.20 (t, J = 47 Hz); C NMR (75
3
MHz, CDCl ) δ 83.9 (d, J = 184 Hz), 124.2, 125.4, 126.8, 128.08,
3
ACKNOWLEDGMENTS
1
28.13, 128.6, 130.3, 131.18, 131.20, 134.0, 196.9 (d, J = 16.7 Hz).
-Fluoro-1-(4-methylphenyl)ethanone (2d): Isolated yield
Table 2, entry 8), 0.0898 g (59%); H NMR (300 MHz, CDCl ) δ
.43 (s, 3H), 5.50 (d, J = 47 Hz, 2H), 7.29 (d, J = 8.3 Hz, 2H), 7.79 (d,
■
1
4
2
This work was partly supported by a Grant-in-Aid for Scientific
Research from the Ministry of Education, Culture, Sports,
Science and Technology of Japan (25410048).
1
(
2
3
19
J = 8.3 Hz, 2H); F NMR (283 MHz, CDCl ) δ −231.60 (t, J = 47
3
Hz); 13C NMR (75 MHz, CDCl ) δ 21.8, 83.5 (d, J = 181 Hz), 127.9
3
REFERENCES
■
(
d, J = 2.5 Hz), 129.6, 131.2, 145.1, 193.0 (d, J = 15.5 Hz).
-(4-Chlorophenyl)-2-fluoroethanone (2e):
Table 2, entry 10), 0.116 g (67%); H NMR (300 MHz, CDCl ) δ
14
(1) (a) Olah, G. A.; Chambers, R. D.; Surya Prakash, G. K. Synthetic
Fluorine Chemistry; John Wiley: New York, 1992. (b) Hudlicky, M.;
Pavlath, A. E. Chemistry of Organic Fluorine Compounds II; American
Chemical Society: Washington, DC, 1995. (c) Chambers, R. D.
Fluorine in Organic Chemistry; Blackwell Publishing: Oxford, U.K.,
1
Isolated yield
1
(
5
2
(
3
.52 (d, J = 47 Hz, 2H), 7.52 (d, J = 8.6 Hz, 2H), 7.90 (d, J = 8.6 Hz,
H); 19F NMR (283 MHz, CDCl ) δ 230.91 (t, J = 47 Hz); C NMR
13
3
75 MHz, CDCl ) δ 83.6 (d, J = 182 Hz), 129.3, 129.4 (d, J = 3.1 Hz),
32.0 (d, J = 1.3 Hz), 140.7, 192.5 (d, J = 16.1 Hz).
-Fluoro-1-(4-methoxyphenyl)ethanone (2f): Isolated yield
Table 2, entry 13), 0.113 g (67%); H NMR (300 MHz, CDCl ) δ
3
2
004.
1
16
(2) (a) Yoneda, N. J. Fluorine Chem. 2004, 125, 7−17. (b) Yusubov,
2
1
M. S.; Zhdankin, V. V. Curr. Org. Synth. 2012, 9, 247−272.
(
3
3
(
3) (a) Zhdankin, V. V. J. Org. Chem. 2011, 76, 1185−1197.
(b) Merritt, E. A.; Olofsson, B. Synthesis 2011, 517−538. (c) Brand, J.
P.; Gonzalez, D. F.; Nicolai, S.; Waser, J. Chem. Commun. 2011, 47,
.93 (s, 3H), 5.51 (d, J = 47 Hz, 2H), 7.00 (d, J = 8.7 Hz, 2H), 7.93 (d,
19
J = 8.7 Hz, 2H); F NMR (283 MHz, CDCl ) δ −230.98 (t, J = 47
3
Hz); 13C NMR (75 MHz, CDCl ) δ 55.5, 83.5 (d, J = 180 Hz), 114.1,
́
3
1
2
2
02−115. (d) Satam, V.; Harad, A.; Rajule, R.; Pati, H. Tetrahedron
010, 66, 7659−7706. (e) Uyanik, M.; Ishihara, K. Chem. Commun.
009, 2086−2099. (f) Zhdankin, V. V. ARKIVOC 2009, 1−62.
(g) Zhdankin, V. V.; Stang, P. J. Chem. Rev. 2008, 108, 5299−5358.
(4) (a) Hara, S.; Sekiguchi, M.; Ohmori, A.; Fukuhara, T.; Yoneda, N.
Chem. Commun. 1996, 1899−1900. (b) Yoshida, M.; Fujikawa, K.;
Sato, S.; Hara, S. ARKIVOC 2003, 36−42.
1
26.8 (d, J = 1.2 Hz), 130.3 (d, J = 3.1 Hz), 164.2, 191.9 (d, J = 15.5
Hz).
-Fluoro-1,2-diphenylethanone (2g): Isolated yield (Table 2,
1
6
2
1
entry 15), 0.120 g (75%); H NMR (300 MHz, CDCl ) δ 6.52 (1d, J =
3
19
4
9 Hz, 1H), 7.38−7.68 (m, 8H), 7.93−7.96 (m, 2H); F NMR (283
1
3
MHz, CDCl ) δ −177.04 (d, J = 49 Hz); C NMR (75 MHz, CDCl3)
3
δ 93.9 (d, J = 184 Hz), 127.4 (d, J = 5.6 Hz), 128.7, 129.04, 129.07 (d,
J = 1.2 Hz), 129.6 (d, J = 2.5 Hz), 133.7, 134.0, 134.2 (d, J = 19.7 Hz),
(
(
2
5) Sato, S.; Yoshida, M.; Hara, S. Synthesis 2005, 2602−2605.
6) (a) Kitamura, T.; Kuriki, S.; Morshed, M. H.; Hori, Y. Org. Lett.
011, 13, 2392−2394. (b) Kitamura, T.; Kuriki, S.; Muta, K.;
Morshed, M. H.; Muta, K.; Hori, Y.; Miyazaki, M. Synthesis 2013, 45,
125−3130.
7) (a) Leroy, J. J. Org. Chem. 1981, 46, 206−209. (b) Moughamir,
K.; Atmani, A.; Mestdagh, H.; Rolando, C.; Francesch, C. Tetrahedron
Lett. 1998, 39, 7305−7306. (c) Makosza, M.; Bujok, R. J. Fluorine
Chem. 2005, 126, 209−216. (d) Fuglseth, E.; Thvedt, T. H. K.; Møll,
M. F.; Hoff, B. H. Tetrahedron 2008, 64, 7318−7323. (e) Chen, Z.;
Zhu, W.; Zhen, Z.; Zou, X. J. Fluorine Chem. 2010, 131, 340−344.
(8) (a) Barnette, W. E. J. Am. Chem. Soc. 1984, 106, 452−454.
(b) Rozen, S.; Brand, M. Synthesis 1985, 665−667. (c) Differding, E.;
Lang, R. W. Tetrahedron Lett. 1988, 29, 6087−6090. (d) Resnati, G.;
DesMarteau, D. D. J. Org. Chem. 1991, 56, 4925−4929. (e) Davis, F.
A.; Han, W. Tetrahedron Lett. 1991, 32, 1631−1634. (f) Davis, F. A.;
Zhou, P.; Murphy, C. K. Tetrahedron Lett. 1993, 34, 3971−3974.
(9) (a) Middleton, W. J.; Bingham, E. M. J. Am. Chem. Soc. 1980,
102, 4845−4846. (b) Purrington, S. T.; Lazaridis, N. V.; Bumgardner,
C. L. Tetrahedron Lett. 1986, 27, 2715−2716. (c) Umemoto, T.;
Kawada, K.; Tomita, K. Tetrahedron Lett. 1986, 27, 4465.
1
94.2 (d, J = 21.7 Hz).
2
1
7
-Fluoro-1-phenyl-1-propanone (2h): Isolated yield (Table 2,
entry 17), 0.107 g (70%); H NMR (400 MHz, CDCl ) δ 1.65 (dd, J =
.8, 24 Hz, 3H), 5.69 (dq, J = 6.8, 48 Hz, 1H), 7.47 (t, J = 7.6 Hz, 2H),
.59 (t, J = 7.6 Hz, 1H), 7.96 (d, J = 7.6 Hz, 2H); F NMR (376
MHz, CDCl ) δ −181.52 (dq, J = 24, 48 Hz); C NMR (100 MHz,
CDCl ) δ 18.4 (d, J = 22.4 Hz), 90.3 (d, J = 178.8 Hz), 128.7, 129.0
d, J = 3.9 Hz), 133.8, 134.0, 197.1 (d, J = 18.6 Hz).
-Fluoro-1-phenyl-1-butanone (2i): Isolated yield (Table 2,
entry 19), 0.116 g (70%); H NMR (400 MHz, CDCl ) δ 1.09 (t, J =
.6 Hz, 3H), 1.91−2.14 (m, 2H), 5.51 (ddd, J = 4.8, 7.6, 49 Hz, 1H),
.49 (t, J = 7.6 Hz, 2H), 7.61 (t, J = 7.6 Hz, 1H), 7.97 (d, J = 7.6 Hz,
1
3
3
(
6
7
19
13
3
3
(
18
2
1
3
7
7
2
1
9
H); 1 F NMR (376 MHz, CDCl ) δ −190.97 (ddd, J = 23, 27, 49
3
3
Hz); C NMR (100 MHz, CDCl ) δ 9.1 (d, J = 3.9 Hz), 26.1 (d, J =
3
2
1
1.7 Hz), 94.8 (d, J 182.7 Hz), 128.7, 128.8 (d, J = 11.4 Hz), 133.7,
34.4, 196.8 (d, J = 19.4 Hz).
1
7,19
2-Fluoro-1-indanone (2j):.
Isolated yield (Table 2, entry 20),
1
0
3
2
.0991 g (66%); H NMR (400 MHz, CDCl ) δ 3.17−3.30 (m, 1H),
3
.59−3.67 (m, 1H), 5.28 (ddd, J = 4.4, 7.8, 51 Hz, 1H), 7.42−7.48 (m,
19
H), 7.67 (t, J = 8 Hz, 1H), 7.81 (d, J = 8 Hz, 1H); F NMR (376
13
MHz, CDCl ) δ −194.06 (ddd, J = 8, 23, 51 Hz); C NMR (100
MHz, CDCl ) δ 33.4 (d, J = 21.6 Hz), 90.5 (d, J = 189.7 Hz), 124.7,
26.8, 128.4, 133.86, 136.3, 149.6, 199.9 (d, J = 14.7 Hz).
-Chloro-2-fluoro-1-phenylethanone (2k):
Table 2, entry 21), 0.107 g (62%); H NMR (400 MHz, CDCl ) δ
.84 (d, J = 50, 1H), 7.53 (t, J = 8 Hz, 2H), 7.67 (t, J = 8 Hz, 1H), 8.08
(10) Thvedt, T. H. K.; Fuglseth, E.; Sundby, E.; Hoff, B. H.
Tetrahedron 2009, 65, 9550−9556.
(11) (a) Stavber, S.; Zupan, M. Tetrahedron Lett. 1996, 37, 3591−
3594. (b) Stavber, S.; Jereb, M.; Zupan, M. Chem. Commun. 2000,
1323−1324. (c) Stavber, G.; Zupan, M.; Stavber, S. Synlett 2009, 589−
594.
3
3
1
2
0
2
Isolated yield
1
(
6
3
D
dx.doi.org/10.1021/jo500691b | J. Org. Chem. XXXX, XXX, XXX−XXX