A convenient preparation of fluorinating reagent F-TEDA bearing bisphenylsulfonylimide counterion and its fluorination to oxindoles

Article abstract of DOI:10.1002/cjoc.201400680

The direct preparation of a kind of fluorinating reagent 1 [F-TEDA-N(SO₂Ph)₂] was realized in high yield via the complexation of N-fluorobenzenesulfonimide (NFSI) with 1-(chloromethyl)-1,4-diazabicyclo[2.2.2]octan-1-ium N',N'-bis-(benzenesulfonylimide) salt. In its fluorination to oxindoles, the fluorinating products 6 were afforded in moderate to high yields.

Full text of DOI:10.1002/cjoc.201400680

FULL PAPER
DOI: 10.1002/cjoc.201400680
A Convenient Preparation of Fluorinating Reagent F-TEDA
Bearing Bisphenylsulfonylimide Counterion and Its
Fluorination to Oxindoles
Wenhua Zhu, Xiaohui Hu, Fajie Wang, Xianjin Yang,* and Xinyan Wu*
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and
Technology, Shanghai 200237, China
The direct preparation of a kind of fluorinating reagent 1 [F-TEDA-N(SO Ph) ] was realized in high yield via
2
2
the complexation of N-fluorobenzenesulfonimide (NFSI) with 1-(chloromethyl)-1,4-diazabicyclo[2.2.2]octan-1-ium
N',N'-bis-(benzenesulfonylimide) salt. In its fluorination to oxindoles, the fluorinating products 6 were afforded in
moderate to high yields.
Keywords fluorinating reagent, fluorination, oxindoles
Introduction
Results and Discussion
Both Selectfluor and NFSI are important and com-
mercial N-F fluorinated reagents. A lot of literatures
Herein, according to Scheme 1, the preparation route
for the designed fluorinating reagent F-TEDA-N(SO Ph)
2 2
is tried. Starting from 2, intermediates 3, 4 were
achieved conveniently in high yields. After that, the
reaction of 4 with NFSI was tried in various solvents.
As shown in Table 1, no product was detected in
[1-4]
have demonstrated their applications
in chemical,
pharmaceutical, agricultural and material fields. For
broadening the more extensive applications and meeting
the more effective requirements, new N-F reagents were
[5]
continually reported and developing novel N-F re-
agents is still meaningful.
CH
O (Entries 1—8); while in MeOH, F NMR moni-
toring shows that F-TEDA-N(SO Ph) was achieved in
11% yield after stirring for 8 d (Entry 9). Fortunately,
F-TEDA-N(SO Ph) was afforded in 83% monitored
2 2
Cl , DMF, EA, EtOH, i-PrOH, MTBE, THF and
1
9
H
2
We envision that a kind of N-F compounds bearing
both Selectfluor and NFSI fragments might display their
common properties. According to this idea, a N-F com-
pound structurally containing bisphenylsulfonylimide
2
2
2
2
yield in MeCN for 8 d (Entry 10).
and triethylenediamine 1 [F-TEDA-N(SO
2
Ph)
2
] is de-
Then the starting material ratios were screened.
Monitored F NMR exposed that starting material ratio
19
signed (Structure A in Figure 1), where the F atom lies
between two nitrogen atoms and a N-F-N three-center-
four-electron bond is formed, then naturally it displays
common chemical characteristics of NFSI and Select-
Scheme 1 Preparation route for 1 [F-TEDA-N(SO Ph) ] from
2
2
NFSI
fluor, or F-TEDA-N(SO
2
Ph)
2
might exist in a salt form
Cl-
-
N(SO
Cl
2 2
Ph)
(
Structure B in Figure 1), and if so, it will behave more
Cl
like Selectfluor than NFSI.
(PhSO ) NNa
N
N
CH
2
Cl
2
N
N
2 2
N
N
2
3
-
4
N(SHO
2
Ph)
2
-
Cl
N(SO
2
Ph)
2
Cl
N
Ph
Ph
S
+
N
+
O
-
N
O
S
N(SO Ph)
2
2
N
N
F
O
-
Cl
F
O
N(SO Ph)
2
2
F
N(SO Ph)2
N
2
B
A
N
solvent
F
N(SO2Ph)2
Figure 1 Designed complex structure containing the skeleton of
Selectfluor and NFSI.
1
*
E-mail: yxj@ecust.edu.cn
Received October 8, 2014; accepted November 11, 2014; published online December 9, 2014.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201400680 or from the author.
220
© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2015, 33, 220—224

A Convenient Preparation of Fluorinating Reagent F-TEDA and Its Fluorination to Oxindoles
Table 1 Preparation of 1 via the reaction of 4 with NFSI in
various solvents
Table 2 Preparation of 1 from the reaction of 4 with NFSI in
various ratios
-
-
2 2
N(SO Ph)
N(SO2Ph)2
Cl
-
-
Cl
N(SO
2
Ph)
2
N(SO Ph)
N
N
2
2
N
Ph
S
Ph
S
Cl
Cl
4
Ph
Ph
S
O
O
N
4
N
N
O
N
N
O
O
S
N
F
Solvent, r.t., 8 d
N
F
O
O
MeCN, r.t., 8 d
O
F
2 2
N(SO Ph)
F
N(SO2Ph)2
NFSI
1
NFSI
1
(F-TEDA-N(SO Ph) )
2 2
1
9
a
b
a
b
c
Entry Solvent
F NMR
1 /%
Entry
4∶NFSI
10∶1
5∶1
Yield /%
0.14
7
Yield /%
100
98
1
2
3
4
5
6
7
8
9
CH
2
Cl
2
−39, −111
−39, −111
N.d
N.d
N.d
N.d
N.d
N.d
N.d
N.d
11
1
2
DMF
EA
−39, −111
3
2∶1
34
91
EtOH
＋39, −39, −111
−49, −92, −111
−39, −111
4
1.5∶1
1∶1
47
85
i-PrOH
MTBE
THF
5
67
83
6
1∶1.5
1∶2
73
58
−39, −111,−150
−39, −111
7
73
43
H O
2
8
1∶5
82
13
MeOH
＋49, ＋39, −39, −100, −111
49, −39, −111
9
1∶10
1∶20
92
7
c
10
CH CN
83
10
92
5
3
a
a
b
NFSI (35 mg, 0.11 mmol), 5 mL of solvent and 4 (50 mg, 0.11
Reaction underwent at room temperature for 8 d. The moni-
mmol) were added into a flask under stirring, then the reaction
system was stirred at room temperature for 8 d. The mixture sys-
tored yield was calculated by the peak area of ClCH2 in
F-TEDA-N(SO Ph) (δ 5.42) divided by the peak area of ClCH
2
2
1
2
1
9
c
tem was monitored by F NMR and gave the monitored yields.
in 4 (δ 5.08) in H NMR. The monitored yield was calculated by
the peak area of F-TEDA-N(SO Ph) divided by the total peak
b
The monitored yield was calculated by the peak area of
2
2
1
9
F-TEDA-N(SO Ph) divided by the total peak area of all peaks.
area of all peaks in F NMR.
2
2
c
NFSI is consumed almost completely with the peak area ratio of
F-TEDA-N(SO Ph) ∶NFSI＝1∶0.02 in the F NMR spectra.
2 2
1
9
of 4∶NFSI changed from 1∶1 to 10∶1 which led to
complete conversion of NFSI to F-TEDA-N(SO Ph)
Entries 1－5 in Table 2). H NMR monitoring indicated
2
2
1
(
that ratio of 4∶NFSI changed from 1∶1 to 1∶20 re-
sulting in 92% conversion of compound 4 to
F-TEDA-N(SO
2
-Ph)
2
(Entries 5, 10 in Table 2).
Ph) (Figure 2),
19
In the F NMR of F-TEDA-N(SO
2
2
chemical shift of fluorine atom was presented at δ 49,
which was very close to the site of Selectfluor (δ 48) but
far away from that of NFSI (δ −39). It demonstrated that
19
Figure 2 The F NMR spectra of compound 1.
Conclusions
2 2
compound F-TEDA-N(SO Ph) will act more like Se-
lectfluor. Solubility test showed that F-TEDA-
N(SO Ph) was resolved easily in H O, MeCN and
In conclusion, a kind of Selectfluor with two
(PhSO ) N as counterions was synthesized via a con-
2 2
−
2
2
2
MeOH, slightly in CH
2
Cl
2
, but not in EA. The melting
venient complexation between NFSI and 1-(chlorometh-
yl)-1,4-diazabicyclo[2.2.2]octan-1-ium N',N'-bis-(ben-
zenesulfonimide) salt in a high yield. Preliminary ex-
point and DSC test indicated F-TEDA-N(SO
begin to melt at 137 ℃ and decompose at 139 ℃.
Furthermore, experiments were made to explore the
fluorinating ability of F-TEDA-N(SO Ph) . 3-Phenyl-2-
oxindoles (5) were chosen to react with F-TEDA-
2 2
Ph) will
2 2
periments demonstrated that F-TEDA-N(SO Ph) exhib-
ited its properties similar to commercial Selectfluor. It is
the first report of the preparation of Selectfluor bearing
bisphenylsulfonylimide counterion. It is also an exam-
ple of preparing a stronger fluorinating reagent from a
weaker fluorinating reagent. The fluorination of oxin-
2
2
[
6]
N(SO Ph) in the presence of (DHQD) ANQ (Table 3).
2
2
2
5
2
Except that 5g (R ＝Me, Entry 9) and 5k (R ＝
p-MeC H and R ＝Me Entry 13) gave the correspond
6 4
3
ing products 6g and 6k in lower yields, other substrates
afforded 6 in good yields. Enantioselectivities were
tested, however the results were bad.
2 2
doles with F-TEDA-N(SO Ph) afforded fluorinating
products 6 in moderate to high yields similar to Select-
fluor and NFSI. Further study on the application of
Chin. J. Chem. 2015, 33, 220—224
© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
221

Zhu et al.
FULL PAPER
Table 3 Fluorination of 2-oxindines (5) with 1
R2
R2
1 (1.2 equiv.),
DHQD) ANQ (5 mol%)
H
R3
R4
F
R3
(
2
O
O
R4
N
CH
2
Cl
2
/CH
3
CN (V:V = 3:4),
N
(6.0 equiv.), -78 o
C
R5
R1
K
2
CO
3
R5
R1
5
6
H
N
HO
H
O
N
(
DHQD)
2
ANQ
1
2
3
4
5
a
b,c
Entry
5 (R /R /R /R /R )
Condition
Yield (ee)/% of 6
72 (62)
66 (77)
74 (55)
74 (6)
1
2
3
4
5
6
7
8
9
5a (BOC/C H /H/H/H)
Selectfluor, 96 h
NFSI, 48 h
1, 96 h
6
5
5a (BOC/C H /H/H/H)
6
5
5a (BOC/C H /H/H/H)
6
5
5b (BOC/p-MeC H /H/H/H)
1, 48 h
6
4
5c (BOC/C H /H/Cl/H)
1, 48 h
82 (4)
6
5
5d (BOC/p-FC H /F/H/H)
1, 48 h
79 (33)
71 (30)
76 (31)
66 (37)
82 (23)
81(23)
6
4
5e (BOC/p-OMeC H /H/H/H)
1, 48 h
6
4
5f (BOC/C H /F/H/H)
1, 48 h
6
5
5g (BOC/C H /H/H/Me)
1, 48 h
6
5
10
11
12
13
5h (BOC/p-FC H /H/H/H)
1, 24 h
6
4
5i (BOC/C H /Me/H/H)
1, 24 h
6
5
5j (BOC/β-naphthyl/H/H/H)
5k (BOC/p-MeC H /Me/H/H)
1, 24 h
80 (31)
69 (55)
6
4
2
1, 48 h
a
Compound 5 (0.16 mmol), F-TEDA-N(SO
Ph)
2
(0.18 mmol), K
2
CO
3
(0.97 mmol) were resolved in CH
2
Cl
2
and MeCN (V∶V＝4∶3, 6
b
c
mL) at −78 ℃ till TLC indicated that the reaction was complete. Separated yields. The absolute configurations of 6 were determined
by comparison with HPLC data in the literature.
F-TEDA-N(SO
2
Ph)
2
is in progress.
for two times. Compound 3 (3 g) was gotten in 75%
yield. A white solid; H NMR (D O, 400 MHz) δ: 5.01
2
1
Experimental
(s, 2H), 3.47－3.43 (m, 6H), 3.17－3.13 (m, 6H).
General information
Preparation of 1-(chloromethyl)-1,4-diazabicyclo-
[
2.2.2]octan-1-ium
N',N'-bisbenzenesulfonylimide
All the starting chemicals were commercially avail-
able and used without further purification, fluorinating
reagents NFSI and Selectfluor were purchased from
salt (4) from 3
3
(0.5 g, 2.5 mmol) and 50 mL MeCN were added
1
into a flask and stirred to get a clear mixture, then
bisphenylsulfonylimide sodium salt (0.81 g, 2.5 mmol)
and another 50 mL of MeCN were added. Small quan-
tity of solid deposited after the reaction system was re-
solved. The mixture system was then filtered after stir-
ring overnight. The filtrate was evaporated under re-
duced pressure at 50 ℃. After the removal of most of
the solvent, the crude solid was cooled and recrystal-
lized. Solid 4 (0.91g) was gotten in 79% yield. A white
Shanghai Science Bio-pharmaceutical Co. Ltd. H NMR,
1
3
19
C NMR and F NMR spectra were recorded on a
Bruker 400 MHz instrument. Flash column chromatog-
raphy was performed using silica gel (300－400 mesh).
Melting points were uncorrected.
Preparation of 1-(chloromethyl)-1,4-diazabicyclo-
[
2.2.2]octan-1-ium chloride (3) from TEDA (2)
TEDA (2.5 g, 22.3 mmol) and CH Cl (45 mL) were
added into a 100 mL three-neck glass flash, then re-
fluxed for 2 h. The mixture was filtered after being
2
2
1
solid; H NMR (D O, 400 MHz) δ: 7.51－7.48 (m, 4H),
2
7.42－7.39 (m, 2H), 7.31－7.26 (m, 4H), 5.00 (s, 2H),
3.45－3.40 (m, 6H), 3.16－3.11 (m, 6H).
2 2
cooled and the filtered cake was washed with CH Cl
222
www.cjc.wiley-vch.de
© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2015, 33, 220—224

A Convenient Preparation of Fluorinating Reagent F-TEDA and Its Fluorination to Oxindoles
Preparation of F-TEDA-N(SO
and NFSI
2
Ph)
2
from compound
(CDCl , 400 MHz) δ: 8.0 (d, J＝8.0 Hz, 1H), 7.53－
3
4
7
2
6
.48 (m, 1H), 7.37 (d, J＝7.6 Hz, 1H), 7.30－7.25 (m,
H), 6.98－6.97 (m, 2H), 6.92 (dd, J＝2.8, 2.4 Hz, 1H),
NFSI (7 g, 22 mmol), 4 (1 g, 2.2 mmol) and 70 mL
19
.83 (d, J＝7.6 Hz, 1H), 3.81 (s, 3H), 1.62 (s, 9H);
, 376 MHz) δ: –145.99 (s, 1F).
N-tert-Butoxycarbonyl-3,5-fluoro-3-(phenyl)-2-
F
MeCN were added into a flask, then stirred for 8 d. The
solvent was removed under reduced pressure, the resi-
due was washed with EA, and the crude product was
gotten in 93% yield and 91% HPLC purity. 5 g NFSI
can be recovered after removal of EA from the EA fil-
trate. The crude solid was recrystalled in EA/MeCN
NMR (CDCl
3
[7a]
1
oxindole (6f): A colorless oil; H NMR (CDCl , 400
3
MHz) δ: 8.02 (ddd, J＝9.0, 4.4, 1.0 Hz, 1H), 7.45－7.30
(m, 5H), 7.25－7.16 (m, 1H), 7.12－7.04 (m, 1H), 1.61
19
(
V∶V＝20∶1) and the product was gotten in 80%
yield and 96% purity. F-TEDA-N(SO Ph) : A white
CN, 400 MHz) δ:
.76－7.73 (m, 8H), 7.48－7.44 (m, 4H), 7.41－7.36
m, 8H), 5.59 (m, 2H), 4.99－4.94 (m, 6H), 4.65－4.61
(s, 9H); F NMR (CDCl , 376 MHz) δ: −115.93 (d, J＝
3
2.7 Hz, 1F), −146.47 (d, J＝2.3 Hz, 1F).
2
2
1
solid; m.p. 133 ℃; H NMR (CD
7
(
(
3
N-tert-Butoxycarbonyl-3-fluoro-3-(phenyl)-7-methyl-
[7a]
1
2-oxindole (6g):
3
A colorless oil; H NMR (CDCl ,
400 MHz) δ: 7.33－7.42 (m, 6H), 7.19－7.24 (m, 2H),
1
9
13
19
m, 6H); F NMR (CD
3
CN, 397 MHz) δ: 48.6;
C
2.32 (s, 3H), 1.63 (s, 9H); F NMR (CDCl , 376 MHz)
3
NMR (D
26.01, 68.94, 57.29 (d, JCF＝15 Hz), 54.66; IR (KBr)
ν: 3038, 2984, 2922, 2853, 1446, 1298, 1274, 1152,
2
O, 100 MHz) δ: 140.80, 132.31, 128.83,
δ: –146.11 (s, 1F).
3
1
N-tert-Butoxycarbonyl-3-fluoro-3-(4-fluorophenyl)-
[
7c]
1
2-oxindole (6h):
A colorless oil; H NMR (CDCl ,
3
−1
1
083, 788, 720, 592, 574, 556 cm .
400 MHz) δ: 8.01 (d, J＝8.3 Hz, 1H), 7.56－7.49 (m,
H), 7.40－7.33 (m, 3H), 7.29 (t, J＝7.5 Hz, 1H), 7.07
1
Fluorination of 2-oxindoles (5) with F-TEDA-
19
(
t, J＝8.4 Hz, 2H), 1.62 (s, 9H); F NMR (CDCl , 376
3
N(SO Ph)
2
2
MHz) δ: −111.54 (d, J＝3.2 Hz, 1F), −142.95 (d, J＝3.7
Hz, 1F).
Compound 5 (0.16 mmol), F-TEDA-N(SO
0.18 mmol) and K CO (0.97 mmol) were resolved in
CH Cl and MeCN (V∶V＝4∶3, 6 mL) at −78 ℃ till
2 2
Ph)
(
2
3
N-tert-Butoxycarbonyl-3-fluoro-3-phenyl-5-methyl-
[7b]
1
2
2
2
4
5
1
1
-oxindole (6i): A colorless oil; H NMR (CDCl ,
3
TLC indicated that the reaction was complete. The
mixture was roughly purified by direct flash column
chromatography with EA as fluent phase. EA solution
was added silica and the solvent was removed under
reduced pressure, then the residue was finely purified by
column chromatography with PE/EA (V∶V＝30∶1) as
fluent phase, then pure compounds 6 were gotten.
00 MHz) δ: 7.87 (d, J＝8.4 Hz, 1H), 7.42－7.33 (m,
H), 7.30 (d, J＝8.4 Hz, 1H), 7.17 (s, 1H), 2.36 (s, 3H),
.61 (s, 9H); F NMR (CDCl , 376 MHz) δ: −145.63 (s,
19
3
F).
N-tert-Butoxycarbonyl-3-fluoro-3-(β-naphthyl)-2-
[7a]
1
oxindole (6j): A colorless oil; H NMR (CDCl , 400
3
MHz) δ: 8.06 (d, J＝8.3 Hz, 1H), 7.91－7.77 (m, 3H),
7.73 (s, 1H), 7.59－7.45 (m, 4H), 7.42 (d, J＝7.6 Hz,
N-tert-Butoxycarbonyl-3-fluoro-3-(phenyl)-2-oxin-
[7a]
1
dole (6a):
A colorless oil; H NMR (CDCl
3
, 400
19
1
H), 7.30 (t, J＝7.5 Hz, 1H), 1.61 (s, 9H); F NMR
MHz) δ: 8.01 (d, J＝8.4 Hz, 1H), 7.53－7.51 (m, 1H),
(
CDCl , 376 MHz) δ: −145.22 (s, 1F).
3
7
9
.40－7.29 (m, 6H), 7.27 (d, J＝6.0 Hz, 1H), 1.62 (s,
1
9
N-tert-Butoxycarbonyl-3-fluoro-3-(4-ethylphenyl)-
H); F NMR (CDCl
3
, 376 MHz) δ: −145.37 (s, 1F).
[7d]
1
5
-methyl-2-oxindole (6k): A colorless oil; H NMR
N-tert-Butoxycarbonyl-3-fluoro-3-(4-methylphenyl)-
[
6b]
1
(CDCl , 400 MHz) δ: 7.86 (d, J＝8.4 Hz, 1H), 7.39 (d,
3
2
4
1
7
-oxindole (6b):
3
A colorless oil; H NMR (CDCl ,
J＝8.4 Hz, 1H), 7.28－7.22 (m, 5H), 2.37 (s, 3H), 2.36
00 MHz) δ: 8.00 (d, J＝8.3 Hz, 1H), 7.53－7.46 (m,
H), 7.40－7.35 (m, 1H), 7.29－7.24 (m, 3H), 7.20－
.18 (m, 2H), 2.35 (s, 3H), 1.60 (s, 9H); F NMR
, 376 MHz) δ: −145.53 (s, 1F).
N-tert-Butoxycarbonyl-3-fluoro-3-(phenyl)-6-chlo-
ro-2-oxindole (6c): A colorless oil; H NMR (CDCl
00 MHz) δ: 1.61 (s, 9H), 7.28 (d, J＝1.6 Hz, 1H), 7.29
d, J＝1.6 Hz, 1H), 7.35－7.31 (m, 2H), 7.41－7.38 (m,
1
9
(
s, 3H), 1.61 (s, 9H); F NMR (CD CN, 376 MHz) δ:
3
1
9
−141.90 (s, 1F).
(CDCl
3
Acknowledgement
[
7a]
1
3
,
The authors are grateful to the National Natural Sci-
ence Foundation of China (No. 21372077) for their fi-
nancial supports.
4
(
3
–
19
H), 8.10 (s, 1H); F NMR (CDCl
3
, 376 MHz) δ:
145.07 (s, 1F).
References
N-tert-Butoxycarbonyl-3-fluoro-3-(4-fluorophenyl)-
[
7b]
1
5
-fluoro-2-oxindole (6d):
, 400 MHz) δ: 8.05 (dd, J＝9.0, 4.2 Hz, 1H),
.37 (dd, J＝8.7, 5.2 Hz, 2H), 7.30－7.19 (m, 1H),
A colorless oil; H NMR
[1] For the major reviews for Selectfluor, see: (a) Zupan, M.; Stavber, S.
Trends Org. Chem. 1995, 57, 629; (b) Banks, R. E. J. Fluorine
Chem. 1998, 87, 1; (c) Banks, R. E.; Besheesh, M. K.; Mo-
hialdin-Khaffaf, S. N.; Sharif, I. J. Chem. Soc., Perkin Trans. 1996,
(CDCl
3
7
7
3
1
9
.16－7.07 (m, 3H), 1.63 (s, 9H); F NMR (CDCl
76 MHz) δ: −111.02 (d, J＝3.4 Hz, 1F), −115.70 (d,
3
,
1
9
, 2069; (d) Lal, G. S.; Pez, G. P.; Syvret, R. G. Chem. Rev. 1996,
6, 1737; (e) Nyffeler, P. T.; Durón, S. G.; Burkart, M. D.; Vincent,
J＝1.9 Hz, 1F), −144.1 (s, 1F).
S. P.; Wong, C.-H. Angew. Chem., Int. Ed. 2004, 44, 192; (f)
Stavber, S. Molecules 2011, 16, 6432.
N-tert-Butoxycarbonyl-3-fluoro-3-(4-methoxy-
[7a]
1
phenyl)-2-oxindole (6e):
A colorless oil; H NMR
[2] For the latest research on Selectfluor, see: (a) Sorokin, V. I.; Poz-
Chin. J. Chem. 2015, 33, 220—224
© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
223

Zhu et al.
FULL PAPER
harskii, A. F.; Ozeryanskii, V. A. J. Fluorine Chem. 2013, 154, 67;
Ma, H.; Nie, J.; Ma, J.-A. Chin. J. Chem. 2012, 30, 47; (f) Zhu,
H.-T.; Liu, G.-S. Acta Chim. Sinica 2012, 70, 2404 (in Chinese).
[5] For major reviews and research for other electrophilic fluorinating
reagents, see: (a) Resnati, G.; DesMarteau, D. D. J. Org. Chem.
1991, 56, 4925; (b) DesMarteau, D. D.; Xu, Z.-Q.; Witz, M. J. Org.
Chem. 1992, 57, 629; (c) Umemoto, T.; Kawada, K.; Tomita, K.
Tetrahedron Lett. 1986, 27, 4465; (d) Umemoto, T.; Fukami, S.;
Tomizawa, G.; Harasawa, K.; Kawada, K.; Tomita, K. J. Am. Chem.
Soc. 1990, 112, 8563; (e) Cahard, D.; Audouard, C.; Plaquevent,
J.-C.; Roques, N. Org. Lett. 2000, 2, 3699; (f) Zhu, C.; Maeno, M.;
Zhang, F.; Shigehiro, T.; Kagawa, T.; Kawada, K.; Shibata, N.; Ma,
J.; Cahard, D. Eur. J. Org. Chem. 2013, 29, 6501.
[6] (a) Ishimaru, T.; Shibata, N.; Horikawa, T.; Yasuda, N.; Nakamura,
S.; Toru, T.; Shiro, M. Angew. Chem., Int. Ed. 2008, 47, 4157; (b)
Zhang, Y.; Yang, X.; Xie, T.; Chen, G.; Zhu, W.; Zhang, X.; Yang,
X.; Wu, X.; He, X.; He, H. Tetrahedron 2013, 69, 4933; (c) Shibata,
N.; Suzuki, E.; Asahi, T.; Shiro, M. J. Am. Chem. Soc. 2001, 123,
7001.
(b) Ito, S.; Terada, N.; Seino, K.; Makihata, D.; Sasaki, A.; Oba, T.
Tetrahedeon Lett. 2013, 54, 5916; (c) Rajawinslin, R. R.; Raihan, M.
J.; Janreddy, D.; Kavala, V.; Kuo, C.-W.; Kuo, T.-S.; Chen, M.-L.;
He, C.-H.; Yao, C.-F. Eur. J. Org. Chem. 2013, 25, 5743; (d) Zhang,
C.; Li, Z.; Zhu, L.; Yu, L.; Wang, Z.; Li, C. J. Am. Chem. Soc. 2013,
1
35, 14082; (e) Stenhagen, I. S. R.; Kirjavainen, A. K.; Forsback, S.
J.; Jørgensen, C. G.; Robins, E. G.; Luthra, S. K.; Solin, O.; Gou-
verneur, V. Chem. Commun. 2013, 49, 1386; (f) Amaoka, Y.; Naga-
tomo, M.; Inoue, M. Org. Lett. 2013, 15, 2160; (g) Mizuta, S.;
Stenhagen, I. S. R.; O'Duill, M.; Wolstenhulme, J.; Kirjavainen, A.
K.; Forsback, S. J.; Tredwell, M.; Sandford, G.; Moore, P. R.; Hui-
ban, M.; Luthra, S. K.; Passchier, J.; Solin, O.; Gouverneur, V. Org.
Lett. 2013, 15, 2648; (h) Jin, Z.; Xu, B.; DiMagno, S. G.; Hammond,
G. B. J. Fluorine Chem. 2012, 143, 226; (i) Liu, Y.; Zhu, J.; Qian, J.;
Xu, Z. J. Org. Chem. 2012, 77, 5411.
[
[
3] For latest major reviews for NFSI, see: Differding, E.; Poss, A. J.;
Cahard, D.; Shibata, N. Encyclopedia of Reagents for Organic Syn-
thesis, John Wiley & Sons, Ltd., 2013, p. 1.
4] For latest research for NFSI, see: (a) Zhang, H.; Pu, W.; Xiong, T.;
Li, Y.; Zhou, X.; Sun, K.; Liu, Q.; Zhang, Q. Angew. Chem., Int. Ed.
[7] (a) Deng, Q.-H.; Wadepohl, H.; Gade, L. H. Chem. Eur. J. 2011, 17,
14922; (b) Zhang, R.; Wang, D.; Xu, Q.; Jiang, J.-J.; Shi, M. Chin. J.
Chem. 2012, 30, 1295; (c) Ishimaru, T.; Shibata, N.; Nagai, J.; Na-
kamura, S.; Toru, T.; Kanemasa, S. J. Am. Chem. Soc. 2006, 128,
16488; (d) Ishimaru, T.; Shibata, N.; Horikawa, T.; Yasuda, S.; Na-
kamura, S.; Toru, T.; Shiro, M. Angew. Chem., Int. Ed. 2008, 47,
4157.
2
013, 125, 2589; (b) Lou, S.; Xu, D.; Xia, A.; Wang, Y.; Liu, Y.; Du,
X.; Xu, Z. Chem. Commun. 2013, 49, 6218; (c) Wu, T.; Cheng, J.;
Chen, P.; Liu, G. Chem. Commun. 2013, 49, 8707; (d) Yuan, Z.-L.;
Peng, H.-H.; Liu, G.-S. Chin. J. Chem. 2013, 31, 908; (e) Liu, C.-B.;
(Zhao, C.)
224
www.cjc.wiley-vch.de
© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2015, 33, 220—224