Page 7 of 9
Plea sDe a dl t oo nn oT tr aa nd sj au cs tt i om n as rgins
DOI: 10.1039/C9DT02150G
Journal Name
F), ‐162.66 (m, 4F, meta‐F). MS‐ (APCI, negative mode) for Crystal Data for 3CF
ARTICLE
3
‐Ga: moiety formula: C40
7 4 5
H F24GaN O,2(C
24GaN O, M = 1243.42; monoclinic, space
C
41
H
4
F
27
N
4
Ga: m/z = 1133.9255 (calculated), 1133.9182 (observed). N); formula: C50
H
5
H
17
F
6
group P2 /c (14), a = 24.567(7) Å, b = 7.523(2) Å, c = 25.895(7) Å, V =
1
3
3
‐1
4
695.3 Å , Z = 4, T = 200 K, D
completeness = 0.957, θ(max) = 25.053, R (reflections) = 0.0754
5775), wR (reflections) = 0.2048 (7951), S = 0.893, Npar = 728, CCDC
c
= 1.75746 g/cm , µ (mm ) = 0.730, Data
Synthesis of 3CF
0.19 g, 1.0 mmol) was dissolved in 5‐10 mL DMF after the solution
was sparged for 5 min under the argon atmosphere Then, methyl–
,2–difluoro–2–(fluorosulfonyl) acetate (FSO CF CO Me) was added
0.13 mL, 1.0 mmol) into the reaction with the reaction being
3
‐Al. A dry portion of 3I‐Al (40 mg, 33 μmol) and CuI
(
(
2
code: CCDC1915746.
2
(
2
2
2
maintained at 100 ℃. The reaction was monitored by TLC, after an
ample time of 10 h, the reaction mixture was quenched and
separated with water and CH Cl (1:1 by volume); then, the solution
2 2
Conflicts of interest
containing the organic phase was purified by doing a silica gel
chromatography in which ethyl acetate and hexane (1: 1 by volume)
constituted the mobile phase. The fluorescent band was clearly
identified by inspection and isolated; the non‐volatile product was
There are no conflicts to declare.
Acknowledgements
Z. G. acknowledges the support of this research by a grant from
recrystallized using CH
2 2
Cl and hexane (1: 1) to afford a pure green
1
solid portion of 3CF ‐Al obtained in a yield of 36 % (11 mg). H NMR
3
(
(
400 MHz, CDCl
3
): δ = 9.27 (s, 1H), 8.46 (overlapping d, 2H), 8.32 the Israel Science Foundation. D.G.C. acknowledges Z.G., the
overlapping d, 2H), 7.32 (unresolved t, 2H, pyridine‐H), 6.66 (broad Schulich Faculty of Chemistry, Technion‐Israel Institute of
1
9
t, 4H, pyridine‐H), 5.32 (broad s, 4H, pyridine‐H). F NMR (377 MHz,
CDCl ): δ = ‐48.54 (q, J = 12.07 Hz , 3F), ‐50.32 (q, J = 11.77 Hz , 3F), ‐
5
Technology, and support from KAIST for facilitating his
sabbatical year.
3
2.92 (s, 3F), ‐137.70 (m, 2F, ortho‐F), ‐138.15 (m, 4F, ortho‐F), ‐
1
52.43 (t, J = 22.28 Hz , 2F, para‐F), ‐152.66 (t, J = 21.70 Hz , 1F, para‐
‐
F), ‐161.51 (m, 2F, meta‐F), ‐163.17 (m, 4F, meta‐F). MS (APCI,
References
negative mode) for C40
024.0003 (observed). MS (APCI, positive mode) for C40
m/z = 1024.9979 (calculated), 1024.9583 (observed).
H
5
+
F
24
N
4
Al: m/z = 1023.9945 (calculated),
1
5 24 4
H F N
Al:
1
(a) S. Fukuzumi. et al, Green. Chem., 2018, 20, 948‐963; (b) X.
Dai, D. W. Chen, W. Y. Zhou. et al, Cat. Commun., 2018, 17,
8
1
5‐89; (c) C. M. White, J. P. Zhao, J. Am. Chem. Soc., 2018, 140,
3988‐14009; (d) J. Jiang, J.‐X. Wang, X.‐T. Zhou. et al, Chem.
Synthesis of 4CF
0.23 g, 1.2 mmol) were dissolved in 5‐10 mL DMF which was sparged
with argon after 5 min. The reagent methyl–2,2–difluoro–2–
fluorosulfonyl) acetate (FSO CF CO Me) (0.16 mL, 1.2 mmol) was
then added into the reaction. The temperature of the reaction
mixture was maintained at 100 ℃. The reaction was monitored by
TLC, after an ample time of 10 h, the reaction mixture was then
quenched and separated with water and CH Cl (1:1 by volume); then
2 2
the organic phase was evaporated. The greenish crude product was
purified by silica gel chromatography with ethyl acetate and hexane
3
‐Al. A dry portion of 4I‐Al (40 mg, 30 μmol) and CuI
Eur. J., 2018, 23, 2666‐2674; (e) F. Burg, M. Gicquel, S.
Breitenlechner. et al, Angew. Chem. Int. Ed., 2018, 57, 2953‐
2
1
(a) P. Adler, C. J. Teskey, D. Kaiser, M. Holy, H. H. Sitte and N.
Maulide, Nat. Chem., 2019, 329‐334; (b) C. Varlow, D. Szames,
K. Dahl, V. Bernard‐Gauthier and N. Vasdev, Chem. Commun.,
(
957; (f) G. Li. et al, Angew. Chem. Int. Ed., 2018, 57, 1251‐
255.
(
2
2
2
2
3
2
018, 54, 11835‐11842; (c) E. P. Gillis, K. J. Eastman, M. D. Hill,
D. J. Donnelly and N. A. Meanwell, J. Med. Chem., 2015, 58,
8
315‐8359; (d) Q. Shen, Y.‐G. Huang, C. Liu, J.‐C. Xiao, Q. Y.
Chen, Y. Guo. J. Fluor. Chem., 2015, 179, 14‐22.
(
1:2 by volume) as the mobile phase. The fluorescent parts were
collected and precipitated/recrystallized by CH Cl and hexane (1:1
‐Al were obtained
): δ = 8.10 (d, JH‐
(a) V. S. Barata, A. Postigo, Coord. Chem. Rev., 2013, 257,
2
2
3
8
4
051‐3069. (b) A. Studer, Angew. Chem. Int. Ed., 2012, 51,
950‐8958. (c) D. A. M. McClinton. et al, Tetrahedron., 1992,
8, 6555‐6566.
by volume); importantly, a pure green solid 4CF
3
1
with a yield of 42% (14 mg). H NMR (400 MHz, C
6
D
6
H
= 4.89 Hz, 2H), 7.91 (d, JH‐H = 4.88 Hz, 2H), 7.36 (s, 1H, pyridine‐H),
4
5
R. W. Taft, Chem. Rev., 1991, 91, 165‐195.
1
9
5
.62 (broad s, 2H, pyridine‐H), 5.11 (broad s, 2H, pyridine‐H)). F
): δ = ‐49.23 (s, 6F), ‐49.30 (s, 6F ), ‐138.72 (m,
F, ortho‐F), ‐150.09 (t, JF‐F = 21.70 Hz, 1F, para‐F), ‐150.30 (t, JF‐F
(a) O. Wagner, J. Thiele, M. Weinhart, L. Mazutis, D. A. Weitz,
R. Haag. Lab. Chip., 2016, 16, 65‐69; (b) M. A. Miller and E. M.
Sletten, Org. Lett., 2018, 20, 6850–6854; (c) H. Wang, J. J. Hu,
X. P. Cai, J. R. Xiao and Y. Y. Cheng, Polym. Chem., 2016, 7,
2319‐2322; (d) C.‐U. Lee, R. Khalifehzadeh, B. Ratner and A. J.
Boydston, Macromolecules., 2018, 51, 1280‐1289.
6 6
NMR (377 MHz, C D
6
=
2
1.01 Hz, 2F, para‐F), ‐160.74 (m, 2F, meta‐F), ‐162.55 (m, 4F, meta‐
‐
F). MS (APCI, negative mode) for C41
H
4
F
27
N
4
Al: m/z = 1091.9815
+
(
calculated), 1091.9836 (observed). MS (APCI, positive mode) for
Al: m/z = 1092.9893 (calculated), 1092.9815 (observed).
6
(a) G. Valero, X. Companyó, R. Rios, Chem. Eur. J., 2011, 17,
41 4 27 4
C H F N
2
6
4
018‐2037. (b) J. A. Ma and D. Cahard, Chem. Rev., 2004, 104,
119‐6146. (c) J. A. Ma and D. Cahard, Chem. Rev., 2008, 108,
203‐4278.
Crystal Data for 3I‐Al: moiety formula: 4(C47
sum formula: C203 27, M = 5662.63; orthorhombic, space
group P2 (19), a = 16.5663(1) Å, b = 22.8606(1) Å, c = 26.4461(1)
Å, V = 10015.55(8) Å , Z = 2, T = 100 K, D
15.778, Data completeness = 1.83/0.99, θ(max)= 74.504, R
reflections) = 0.0463 (19527), wR (reflections) = 0.1190 (20347), S
1.037, Npar = 1421, CCDC code: CCDC1868043.
3 6 5 5
H15AlF15I N ), 3(C H N);
7
8
X. Zhan. et al, Inorg. Chem., 2019, 58, 6184‐6198.
4 60 12
H75Al F I N
(a) Y. Kobayashi, I. Kumadaki and S. Kuboki, J. Fluor. Chem.,
1 1 1
2 2
1
982, 19, 517‐520. (b) J. Leroy, J. Fluor. Chem., 1991, 53, 61‐
3
‐3
‐1
c
= 1.87757 g cm , µ (mm )
70. (c) K. E. Thomas, L. J. McCormick. et al, Angew. Chem.‐Int.
Edit., 2017, 56, 10088‐10092. (d) S. Shimizu, N. Aratani and A.
Osuka, Chem.‐Eur. J., 2006, 12, 4909‐1918. (e) Y. Terazono and
D, Dolphin, J. Org. Chem., 2003, 68, 1892‐1900. (f) S. Kang. et
al, Chem.‐Asian J., 2008, 3, 2065‐2074.
=
(
2
=
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