A Cu(I)-promoted one-pot 'SNAr-click reaction' of fluoronitrobenzenes

Article abstract of DOI:10.1016/j.tet.2009.03.035

A one-pot two-step sequence involving a nucleophilic aromatic substitution (S_NAr) of activated fluorobenzenes with azide nucleophile and in situ Huisgen cycloaddition of the resulting aryl azides with alkynes has been developed for a rapid acce

Full text of DOI:10.1016/j.tet.2009.03.035

Tetrahedron 65 (2009) 3974–3979
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A Cu(I)-promoted one-pot ‘SNAr–click reaction’ of fluoronitrobenzenes
*
Kulbhushan A. Dururgkar, Rajesh G. Gonnade, C.V. Ramana
National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411008, Maharashtra, India
a r t i c l e i n f o
a b s t r a c t
Article history:
A one-pot two-step sequence involving a nucleophilic aromatic substitution (SNAr) of activated fluoro-
benzenes with azide nucleophile and in situ Huisgen cycloaddition of the resulting aryl azides with
alkynes has been developed for a rapid access to 1,4-substituted triazoles. Control experiments revealed
that both the steps are catalyzed by Cu(I) and also the course of reaction as SNAr followed by [3þ2]-
cycloaddition.
Received 14 December 2008
Received in revised form 9 March 2009
Accepted 13 March 2009
Available online 21 March 2009
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction
a solvent considering the dependence of rate of SNAr reactions on the
solvent employed.10 The reactions (Table 1, entries 1–3) were slug-
The nucleophilic substitution reaction (SNAr) of activated aryl
halides is an important transformation for C–C and C–heteroatom
bond formation with aryl rings.1 These reactions are facilitated by
the presence of ꢀM groups like a nitro or a carbonyl ortho or para to
the leaving group in general and with meta isomers in some rare
cases.2 Various carbon and heteroatom nucleophiles have been
employed in this context.3 Reports concerning the azide as a nu-
cleophile in SNAr were mainly limited to the mechanistic
investigations.4–6 In a recent publication,7 we showed that 1,4-
diaryltriazoles can be prepared in one pot from SNAr of o- and
p-fluoronitrobenzenes with NaN3 and subsequent Cu-mediated
Huisgen [3þ2] cycloaddition8 of intermediate aryl azides9 with
phenyl acetylene and with 2-, 3-, and 4-bromophenyl acetylenes
(Fig. 1). Herein we describe a complete compilation of our in-
vestigations on a one-pot ‘SNAr–click reaction’ and the control
experiments establishing the course of the reactions.
gish (heated at 70 ꢁC for 1–3 days) and resulted inproducts with poor
yields. The major product isolated was cycloadduct of phenyl acety-
lenewith sodium azide (4-phenyl-1H-1,2,3-triazole, 5a).11 In the case
of 2-nitrofluorobenzene (1a) we could isolate 1,4-diaryltriazole (3aa)
in only 13% yield.6 The SNAr of m-isomer 1b gave exclusively 5awhen
the reactionwas conducted at 70 ꢁC and when heated at 120 ꢁC, a 1:1
mixture of 1,4- and 1,5-diaryl triazoles 3ba12 and 4ba13 was isolated
in 6% yield.14 In the case of 4-nitrofluorobenzene (1c), after 2 days at
70 ꢁC, a 1:1 mixture of 1,4-disubstituted triazole 3ca15 and 1,5-di-
substituted triazole 4ca16 in 10% yield was obtained.14
The yields and the regioselectivity dramatically improved when
the reactions were carried out under standard ‘click reaction’ con-
ditions.9a The employed conditions involve the heating of a sus-
pension of fluoronitrobenzene (1 equiv), phenyl acetylene (1 equiv)
in 9:1 DMSO–H2O, L-proline (20 mol %), Na2CO3 (20 mol %), NaN3
(1.2 equiv), sodium ascorbate (10 mol %), and CuSO4$5H2O (5 mol %)
until the completion of the reaction. In the case of 1-fluoro-2-
nitrobenzene (1a) the yield increased from 13% to 79%. The substrate
1-fluoro-3-nitrobenzene (1b) was difficult to substitute even under
harsh conditions and yielded regioselectively 1-(3-nitrophenyl)-4-
phenyl-1H-1,2,3-triazole (3ba) in 11% yield. The one-pot ‘SNAr–click
reaction’ of 1-fluoro-4-nitrobenzene (1c) was slow and took nearly
2 days for completion and gave exclusively 1,4-isomer 3ca in 75%
yield.
2. Results and discussion
Initially, the SNAr of 2-, 3-, and 4-nitrofluorobenzenes (1a–1c)
with NaN3 and phenyl acetylene (2a) as the dipolarophile was
attempted in the absence ofanyadditives. DMSO hasbeen selected as
As a control, the SNAr of fluoronitrobenzenes 1a–1c was carried
out with the triazole 5a (entries 8–10) under similar conditions. The
reactions in general were sluggish and resulted in poor yields re-
vealing the activation of SNAr by Cu(I) catalyst17 and also that the
sequence of reactions as SNAr followed by cycloaddition. To obtain
more information about the role of Cu(I) catalyst on SNAr, the azide
displacement reactions of 1a–1c were carried out under click
conditions at room temperatures. The reactions were smooth and
took 6 h (1a) and 12 h (1c) and provided the corresponding azido
Br
F
NO2
-
N3
Br
NO2
+
N
N
N
Figure 1. One-pot SNAr–click reaction for 1,4-diaryltriazoles.
* Corresponding author. Tel.: þ91 20 25902577; fax: þ91 20 25902629.
E-mail address: vr.chepuri@ncl.res.in (C.V. Ramana).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.03.035

K.A. Dururgkar et al. / Tetrahedron 65 (2009) 3974–3979
3975
Table 1
Optimization of one-pot SNAR with azide and azide–alkyne cycloaddition
Table 2
The one-pot ‘SNAr–click reaction’ employing functionalized alkynes 2b–2m
N
NaN3 (1.2 eq)
N
N
F
N
Ph
CuSO4.5H2O (5 mol%)
Na Ascorbate (10 mol%)
N
Ph
Ph
O2N
2-NO2 1a
3-NO2 1b
4-NO2 1c
+ HN
N
O2N
R
O2N
2a
+
N
+
O2N
O
N
R
a/b/c
L-Pro (20 mol%)
Na2CO3 (20 mol%)
DMSO:H2O (9:1), 70 °C
24 h (1a) or 48 h (1c)
F
5a
3aa - 3ca
or
1
2
3
+
N
N
N
5a
NO2
Br
F
F
NO2
Cl
O2N
Ph
Br
O
4aa - 4ca
I
NO2
N
NO2
Br
1d
1e
1f
O
Entry
Reactants
Conditions (time/temp)
Products/yield
2g
2b
2c
2d
2e
2f
3
4
5
O
O
O
O
O
O
1
2
3
4
5
6
7
8
1a
1b
1b
1c
1a
1b
1c
1a
1b
1c
1d
2a
a (24 h/70 ꢁC)
a (72 h/70 ꢁC)
a (72 h/120 ꢁC)
a (48 h/70 ꢁC)
b (24 h/70 ꢁC)
b (72 h/120 ꢁC)
b (48 h/70 ꢁC)
c (48 h/70 ꢁC)
c (72 h/120 ꢁC)
c (48 h/70 ꢁC)
b (24 h/70 ꢁC)
13%
d
d
d
3%
5%
d
d
d
d
d
d
d
67%
71%
89%a
87%a
d
OH
O
OBn
2a
2a
2a
2a
2a
2a
5a
5a
5a
2a
O
3%
5%
79%
11%
75%
9%
OH
13
O
O
OBn
OH
O
67%
d
2j
2h
2i
2k
2l
2m
d
9
10
11
d
d
Entry
Reactants
Product
Yield
4%
71%
d
1
2
3
4
5
6
7
8
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1c
1c
1c
1c
1c
1c
1c
2b
2c
2d
2e
2f
3ab
3ac
3ad
3ae
3af
61%
64%
65%
71%
57%
68%
73%
71%
79%
65%
71%
78%
83%
81%
81%
61%
63%
61%
71%
d
N
N
N
Ph
3ea
12
13
1e
2a
b (24 h/70 ꢁC)
15%
61%
2g
2h
2i
3ag
3ah
3ai
O
15%
9
2j22
3aj
3ak
3al
2k23
2l24
2m25
2d
N
10
11
12
13
14
15
16
17
18
19
N
N
Ph
3fa
3am
3cd
3ce
3cf
3cg
3ch
3ci26
3cm
1f
2a
b (24 h/70 ꢁC)
I
NO2
61%
2e
2f
2g
2h
2i
2m
Reagents and Conditions: a) NaN3, DMSO-H2O; b) NaN3, DMSO-H2O, CuSO4.5H2O,
Na ascorbate, L-Proline, Na2CO3; c) 5a, under conditions b.
a
Yields base on HPLC.
benzenes in 79% and 91%, respectively. With 1b, starting compound
remained unchanged even at 60 ꢁC. As expected, the azide dis-
placement reactions of 1a and 1c without any additives were not
facile and starting compounds remain unchanged even after pro-
longed heating. Thus, the room temperature azido displacement
with 1a and 1c under click reaction conditions revealed a signifi-
cant role of Cu(I) catalyst over the SNAR reactions.
The one-pot ‘SNAr–click reactions’ of 1a and 1c have been gen-
eralized by employing various functionalized terminal alkynes,
which include the nitroaryl alkynes, long chain aliphatic alkynes,
and various sugar derived alkynes. The reactions are smooth and
resulted exclusively with 1,4-disubstituted-1,2,3-triazoles (Table 2).
The reaction is even applicable for chloro displacement, as in the
case of 1-chloro-2-nitrobenzene (1d, entry 11). With the less acti-
vated 2-fluorobenzaldehyde (1e, entry 12), the SNAr reaction was
sluggish and the corresponding 1,4-diaryltriazole 3ea was obtained
in poor yield. The 1-fluoro-4-iodo-2-nitrobenzene (1f, entry 13) has
been employed as a substrate to find out the compatibility of other
leaving groups and found that fluorine was displaced selectively
leaving the iodo group intact. The structural characterization of all
the compounds was carried out with the help of spectral and an-
alytical data and the structures of 4ba, 3fa, and 3ch (Table 2, entry
17) were further confirmed by single crystal X-ray structural anal-
yses (Fig. 2a and b).18–20
3. Conclusions
To conclude, a three-component one-pot ‘SNAr–click reaction’
has been explored by employing o- and p-nitrofluorobenzenes and
a diverse set of alkynes. Control experiments reveal the course of
the reaction as SNAr with azide nucleophile followed by the cy-
cloaddition of the resulting nitroazidobenzene intermediate and
both the reactions being catalyzed by Cu(I). The reactions are
generally regioselective and various commonly employed protect-
ing groups are found to be compatible with the conditions
employed.
When we are at an advanced stage, the SNAr of o-fluoronitro-
benzene employing Cu(I) generated in situ by redox process was
reported.6 It has been indicated that when Cu(I) catalyst (in tBuOH
solvent) was employed directly, the reactions resulted in poor
yields. This is anticipated by considering the dramatic influence of
solvents on the rate of aromatic nucleophilic substitution reactions
of azide ion, which indeed has been verified theoretically.21
4. Experimental
4.1. General methods
All experiments involving the heating of NaN3 solutions were per-
formed in a well-ventilated fume hood and behind a blast shield.

3976
K.A. Dururgkar et al. / Tetrahedron 65 (2009) 3974–3979
(3ꢂ25 mL). Organic layer was dried over sodium sulfate and con-
centrated under reduced pressure. The crude solid was purified by
column chromatography over 60–120 silica gel using ethyl acetate–
light petroleum (1:4) to obtain white to yellow solids (65–77%).
4.3.1. 1-(2-Nitrophenyl)-4-phenyl-1H-1,2,3-triazole6 (3aa)
Mp: 140–141 ꢁC (lit. 144–145 ꢁC). IR (Nujol):
n
3143, 2725, 1641,
1605, 1526, 1507, 1462, 1376, 1356, 1227 cmꢀ1. 1H NMR (500 MHz,
DMSO-d6)
7.40 (tt, J¼1.2, 7.3 Hz, 1H), 7.49–7.53 (m, 2H), 7.87 (ddd,
d
J¼2.2, 7.1, 9.1 Hz,1H), 7.94–7.97 (m, 2H), 7.98–8.02 (m, 2H), 7.87 (dd,
J¼1.0, 8.1 Hz,1H), 9.20 (s,1H). 13C NMR (125 MHz, DMSO-d6)
d 120.7
(d), 125.4 (d, 2C), 125.6 (d), 127.4 (d), 128.5 (d), 129.1 (d, 3C), 129.8
(s), 131.3 (s), 134.5 (d), 144.0 (s), 147.1 (s). Anal. Calcd for
C14H10N4O2: C, 63.15; H, 3.79; N, 21.04. Found: C, 62.99; H, 3.67; N,
21.19.
4.3.2. 1-(3-Nitrophenyl)-4-phenyl-1H-1,2,3-triazole12 (3ba)
Mp: 204–205 ꢁC (lit. 198–200 ꢁC). 1H NMR (200 MHz, CDCl3)
d
7.41–7.54 (m, 3H), 7.78 (t, J¼8.21 Hz, 1H), 7.91–7.96 (m, 2H), 8.25–
8.36 (m, 2H), 8.32 (s, 1H), 8.66 (t, J¼2.15 Hz, 1H). 13C NMR (50 MHz,
DMSO-d6)
d 115.0 (d), 120.4 (d), 123.5 (d), 125.8 (d, 2C), 126.3 (d),
128.9 (d), 129.5 (d, 2C), 130.2 (s), 132.0 (d), 137.5 (s), 148.1 (s), 148.9
(s). Anal. Calcd for C14H10N4O2: C, 63.15; H, 3.79; N, 21.04. Found: C,
63.06; H, 3.88; N, 20.89.
4.3.3. 1-(3-Nitrophenyl)-5-phenyl-1H-1,2,3-triazole13 (4ba)
Mp: 133–134 ꢁC. 1H NMR (200 MHz, CDCl3)
d
7.21–7.26 (m, 2H),
7.37–7.43 (m, 3H), 7.58–7.66 (m, 1H), 7.71 (td, J¼1.8, 8.2 Hz, 1H), 7.87
(s,1H), 8.28–8.32(m, 2H).13CNMR(125 MHz, CDCl3)
120.1(d),123.7
d
(d),126.1 (d),128.8 (d, 2C),129.3 (d, 2C),130.0 (d),130.3 (d),130.4 (d),
133.9 (s), 137.6 (s), 137.9 (s), 148.7 (s). Anal. Calcd for C14H10N4O2: C,
63.15; H, 3.79; N, 21.04. Found: C, 63.21; H, 3.75; N, 20.97.
Figure 2. The molecular structures of compounds (a) 4ba, (b) 3fa, and (c) 3ch.
Crystal data for 4ba (C14H10N4O2): M¼266.26, crystal
dimensions 0.62ꢂ0.23ꢂ0.01 mm3, monoclinic, space group
During the work up, use of strong acids and also dichloromethane is
avoided. The reactions were carried out in DMSO (distilled from
CaH2 prior to use) under argon atmosphere. Column chromatog-
raphy was carried out by using Spectrochem silica gel (60–120
P21/n, a¼7.533(11), b¼18.94(3), c¼9.546(14) Å,
b
¼98.37(3)ꢁ,
V¼1347(3) Å3, Z¼4; rcalcd¼1.313 g cmꢀ3
,
m
(Mo K
a
)¼0.092 mmꢀ1
,
F(000)¼552, T¼297(2) K, 2qmax¼50.00ꢁ, 6348 reflections col-
mesh). Specific optical rotations [a]
are measured at 25 ꢁC and
lected, 2346 unique, 1322 observed (I>2s(I)) reflections, 221 re-
D
given in 10ꢀ1 deg cm2 gꢀ1. Infrared spectra were recorded in CHCl3
or Nujol and reported in wave number (cmꢀ1). 1H and 13C NMR
chemical shifts are reported in CDCl3 or DMSO-d6 with CHCl3
(7.27 ppm for 1H, 77 ppm for 13C) and DMSO (2.50 ppm for 1H,
39.5 ppm for 13C) as standards and coupling constants (J) are
reported in hertz (Hz). The following abbreviations are used to
designate signal multiplicity: s¼singlet, d¼doublet, t¼triplet,
q¼quartet, m¼multiplet, br¼broad.
fined parameters, R value 0.0542, wR2¼0.1111 (all data R¼0.1090,
wR2¼0.1366), S¼1.002, minimum and maximum transmission
0.9450 and 0.9991, respectively, maximum and minimum re-
sidual electron densities þ0.216and ꢀ0.169 e Åꢀ3
.
4.3.4. 1-(4-Nitrophenyl)-4-phenyl-1H-1,2,3-triazole15 (3ca)
Mp: 236–238 ꢁC. IR (CHCl3):
3018, 2925, 2855, 1598, 1521,
1348, 1215, 855, 759 cmꢀ1 1H NMR (200 MHz, DMSO-d6)
7.41–
7.56 (m, 3H), 7.93–7.98 (m, 2H), 8.23–8.28 (m, 2H), 8.47–8.51 (m,
2H), 9.48 (s, 1H). 13C NMR (125 MHz, DMSO-d6)
120.1 (d), 120.6 (d,
n
.
d
4.2. General procedure A (products precipitate from the
reaction mixture)
d
2C), 125.5 (d, 2C), 125.7 (d, 2C), 128.7 (d), 129.2 (d, 2C), 129.8 (s),
140.9 (s), 146.8 (s), 148.0 (s). Anal. Calcd for C14H10N4O2: C, 63.15; H,
3.79; N, 21.04; Found: C, 63.31; H, 3.53; N, 20.91.
Fluoronitrobenzene (100 mg, 0.71 mmol) was mixed with phe-
nyl acetylene (72 mg, 0.71 mmol) in 9:1 DMSO–H2O (10 mL). To the
mixture were added L-proline (16 mg, 0.142 mmol), Na2CO3 (15 mg,
0.142 mmol), NaN3 (55 mg, 0.852 mmol), sodium ascorbate (14 mg,
0.071 mmol), and CuSO4$5H2O (9 mg, 0.036 mmol). The mixture
was stirred for 24–48 h at 70 ꢁC (bath temperature) and then the
mixture was poured into 30 mL of ice-cold water. The solid residue
was filtered and crystallized from appropriate solvent systems to
procure white to yellow crystalline solids in 57–83% yield.
4.3.5. 1-(4-Nitrophenyl)-5-phenyl-1H-1,2,3-triazole16 (4ca)
Mp: 165–166 ꢁC. 1H NMR (200 MHz, CDCl3)
d
7.21–7.26 (m, 2H),
7.36–7.46 (m, 3H), 7.54–7.61 (m, 2H), 7.86 (s,1H), 8.26–8.34 (m, 2H).
13C NMR (125 MHz, DMSO-d6)
126.0 (d), 126.1 (d), 127.5 (d, 2C),
d
127.8 (d, 2C), 128.3 (d, 2C), 130.1 (d, 2C), 130.1 (s), 140.9 (s), 144.7 (s),
146.2 (s). Anal. Calcd for C14H10N4O2: C, 63.15; H, 3.79; N, 21.04.
Found: C, 63.11; H, 3.73; N, 20.97.
4.3. General procedure B (3aa, 4ba, 4ca, 3ad, 3ai, 3ak, 3al, 3am,
3cd, 3cm: products purified by column chromatography)
4.3.6. 2-(4-Phenyl-1H-1,2,3-triazol-1-yl)benzaldehyde (3ea)
IR (Nujol):
NMR (500 MHz, CDCl3)
n
3017, 1696, 1601, 1456, 1216, 1024, 694, 667 cmꢀ1. 1H
d
7.39–7.49 (m, 3H), 7.58 (dd, J¼1.4, 7.8 Hz,
The reactions were carried out as described above and after
completion, the contents were poured into 30 mL of water and
combined water layer was thoroughly extracted with ethyl acetate
1H), 7.66–7.70 (m, 1H), 7.75–7.82 (m, 2H), 7.92–7.94 (m, 1H), 8.13
(dd, J¼1.6, 7.7 Hz, 1H), 8.19 (s, 1H), 9.99 (s, 1H). 13C NMR (125 MHz,
CDCl3)
d 121.5 (d), 125.3 (d), 125.9 (d, 2C), 128.7 (d), 129.0 (d, 2C),

K.A. Dururgkar et al. / Tetrahedron 65 (2009) 3974–3979
3977
129.5 (s), 129.6 (d), 130.1 (d), 130.4 (s), 134.7 (d), 138.3 (s), 148.5 (s),
188.5 (d). Anal. Calcd for C15H11N3O: C, 72.28; H, 4.45; N, 16.86.
Found: C, 72.31; H, 4.49; N, 16.80.
(m, 1H). 13C NMR (100 MHz, CDCl3)
d
121.0 (d), 122.7 (s), 125.6 (d),
127.5 (d, 2C), 127.9 (d), 129.8 (s), 130.8 (d), 132.2 (d, 2C), 132.4 (s),
133.8 (d), 144.4 (s), 147.4 (s). Anal. Calcd for C14H9BrN4O2: C, 48.72;
H, 2.63; Br, 23.15; N, 16.23. Found: C, 48.44; H, 2.40; Br, 23.11; N,
16.41.
4.3.7. 1-(4-Iodo-2-nitrophenyl)-4-phenyl-1H-1,2,3-triazole (3fa)
Mp: 199–201 ꢁC. IR (Nujol):
n
2926, 2854, 146, 1377, 1215, 764,
669 cmꢀ1.1H NMR (200 MHz, DMSO-d6)
d
7.23–7.40 (m, 3H), 7.57 (d,
4.3.13. 2-((1-(2-Nitrophenyl)-1H-1,2,3-triazol-4-yl)methyl)-
J¼8.1 Hz, 1H), 7.81–7.91 (m, 2H), 8.16 (d, J¼7.3 Hz, 1H), 8.33 (s, 1H),
isoindoline-1,3-dione (3ag)
8.80 (s, 1H). 13C NMR (100 MHz, CDCl3þDMSO-d6)
d
93.6 (s), 120.3
Mp: 213–214 ꢁC. IR (Nujol):
n
2921, 2724, 1765, 1717, 1586, 1604,
1528, 1463, 1376, 1312, 1041, 934, 714 cmꢀ1 1H NMR (200 MHz,
DMSO-d6) 4.95 (s, 2H), 7.77–7.96 (m, 7H), 8.16–8.21 (m, 1H), 8.68
(s, 1H). 13C NMR (125 MHz, DMSO-d6)
32.9 (t), 123.4 (d, 2C), 124.7
(d),124.0 (d, 2C),126.7 (d),126.9 (d),127.2 (d, 2C),127.4 (s),128.2 (s),
132.0 (d), 141.2 (d), 142.5 (s), 146.0 (s). Anal. Calcd for C14H9IN4O2: C,
42.88; H, 2.31; N, 14.29. Found: C, 42.93; H, 2.27; N, 14.24.
.
d
d
Crystal data for 3fa (C14H9IN4O2): M¼392.15, crystal
(d), 125.6 (d), 127.6 (d), 129.1 (s), 131.3 (d), 131.7 (s), 134.5 (d), 134.8
(d, 2C), 143.4 (s, 2C), 144.1 (s), 167.5 (s, 2C). Anal. Calcd for
C17H11N5O4: C, 58.45; H, 3.17; N, 20.05; Found: C, 58.50; H, 3.20; N,
20.10.
dimensions 0.68ꢂ0.15ꢂ0.05 mm3, monoclinic, space group P21/c,
a¼5.5301(12),
b¼17.085(4),
c¼15.094(3) Å,
b
¼93.124(4)ꢁ,
V¼1424.0(5) Å3, Z¼4; rcalcd¼1.829 g cmꢀ3
,
m
(Mo K
a
)¼2.258 mmꢀ1
,
F(000)¼760, T¼297(2) K, 2qmax¼50.00ꢁ, 7072 reflections col-
lected, 2501 unique, 1831 observed (I>2
s
(I)) reflections, 190 re-
4.3.14. 2-(1-(2-Nitrophenyl)-1H-1,2,3-triazol-4-yl)propan-
fined parameters, R value 0.0548, wR2¼0.1245 (all data R¼0.0762,
wR2¼0.1362), S¼1.094, minimum and maximum transmission
0.3089 and 0.8955, respectively, maximum and minimum residual
2-ol (3ah)
Mp: 111–113 ꢁC. IR (Nujol):
n
3349, 3149, 2924, 1607, 1538, 1506,
1462, 1376,1362,1234 cmꢀ1. 1H NMR (200 MHz, DMSO-d6)
d
1.53 (s,
electron densities þ1.454 and ꢀ0.679 e Åꢀ3
.
6H), 5.34 (s, 1H), 7.76–7.82 (m, 1H), 7.84–7.85 (m, 1H), 7.89–7.98 (m,
1H), 8.18 (dd, J¼1.4, 8.1 Hz, 1H), 8.45 (s, 1H). 13C NMR (50 MHz,
4.3.8. 1,4-Bis(2-nitrophenyl)-1H-1,2,3-triazole (3ab)
Mp: 215–216 ꢁC. IR (CHCl3): 2924, 2854,1377, 761 cmꢀ1.1H NMR
(500 MHz, DMSO-d6) 7.83 (t, J¼7.5 Hz, 1H),
7.69 (t, J¼7.3 Hz, 1H),
7.87–7.91 (m, 2H), 7.96–8.02 (m, 3H), 8.27 (d, J¼7.8 Hz, 1H), 9.15 (s,
1H). 13C NMR (125 MHz, DMSO-d6)
122.7 (s), 124.3 (d), 125.0 (d),
DMSO-d6) d 30.7 (q, 2C), 67.2 (s), 121.9 (d), 125.5 (d), 127.2 (d), 129.4
n
(s), 130.8 (d), 134.3 (d), 144.2 (s), 156.8 (s). Anal. Calcd for
C11H12N4O3: C, 53.22; H, 4.87; N, 22.57. Found: C, 53.18; H, 4.82; N,
22.52.
d
d
d
125.7 (d), 127.7 (d), 128.8 (s), 130.0 (d), 130.6 (d), 131.6 (d), 132.8 (d),
134.6 (d), 142.6 (s), 144.0 (s), 148.2 (s). Anal. Calcd for C14H9N5O4: C,
54.02; H, 2.91; N, 22.50. Found: C, 53.98; H, 2.88; N, 22.46.
4.3.15. 2-(1-(2-Nitrophenyl)-1H-1,2,3-triazol-4-yl)ethanol (3ai)
Mp: 92–93 ꢁC. IR (Nujol):
n
3326, 3137, 2724, 1605, 1536, 1503,
1460, 1376, 1365, 1241 cmꢀ1. 1H NMR (200 MHz, DMSO-d6)
d
2.88 (t,
J¼6.9 Hz, 2H), 3.67–3.75 (m, 2H), 4.83 (t, J¼5.1 Hz,1H) 7.76–7.81 (m,
1H), 7.84 (d, J¼0.8 Hz, 1H), 7.89–7.98 (m, 1H), 8.15–8.20 (m, 1H),
4.3.9. 1-(2-Nitrophenyl)-4-(4-nitrophenyl)-1H-1,2,3-triazole (3ac)
Mp: 290–292 ꢁC. IR (Nujol):
n
3147, 1604, 1534, 1511, 1459, 1339,
8.43 (s, 1H). 13C NMR (50 MHz, DMSO-d6)
d 29.1 (t), 60.3 (t), 123.8
1108, 1024, 854, 756 cmꢀ1
.
1H NMR (400 MHz, DMSO-d6)
d
7.88–
(d), 125.5 (d), 127.2 (d), 129.4 (s), 130.9 (d), 134.3 (d), 144.2 (s), 145.7
(s). Anal. Calcd for C10H10N4O3: C, 51.28; H, 4.30; N, 23.92. Found: C,
51.34; H, 4.35; N, 23.84.
7.92 (m, 1H), 7.99–8.05 (m, 2H), 7.21 (d, J¼8.5 Hz, 2H), 8.28 (d,
J¼8.0 Hz, 1H), 8.39 (d, J¼8.8 Hz, 2H), 9.45 (s, 1H). 13C NMR
(125 MHz, DMSO-d6)
d 124.6 (d, 2C), 124.9 (d), 125.8 (d), 126.3 (d,
2C), 127.6 (d), 128.9 (s), 131.6 (d), 134.7 (d), 136.2 (s), 144.0 (s), 145.2
(s), 147.0 (s). Anal. Calcd for C14H9N5O4: C, 54.02; H, 2.91; N, 22.50.
Found: C, 54.10; H, 2.87; N, 22.44.
4.3.16. 15-(1-(2-Nitrophenyl)-1H-1,2,3-triazol-4-yl)pentadecan-
1-ol (3aj)
Mp: 95–96 ꢁC. IR (CHCl3):
n
3420, 3019, 2928, 2855, 2400, 1610,
1538, 1505, 1466, 1354, 1215, 1042, 7557, 668 cmꢀ1 1H NMR
(500 MHz, DMSO-d6) 1.22 (s, 18H), 1.31–1.34 (m, 4H), 1.38
.
4.3.10. 4-(2-Bromophenyl)-1-(2-nitrophenyl)-1H-1,2,3-
d
triazole (3ad)
(q, J¼6.6 Hz, 2H), 1.65 (q, J¼7.3 Hz, 2H), 2.70 (t, J¼7.4 Hz, 2H), 3.35
(dd, J¼6.2, 11.8 Hz, 2H), 4.35 (t, J¼4.9 Hz, 1H), 7.79–7.84 (m, 2H),
7.93 (t, J¼7.7 Hz, 1H), 8.17 (d, J¼7.8 Hz, 1H), 8.42 (s, 1H). 13C NMR
Mp: 125 ꢁC. 1H NMR (400 MHz, CDCl3)
d
7.24 (dt, J¼1.7, 7.8 Hz,
1H), 7.46 (dt, J¼1.2, 7.8 Hz,1H), 7.68 (dd, J¼1.0, 8.1 Hz,1H), 7.73 (br s,
1H), 7.75 (br s,1H), 7.83 (dt, J¼1.6, 8.1 Hz,1H), 8.12 (dd, J¼1.5, 8.2 Hz,
1H), 8.24 (dd, J¼1.8, 7.8 Hz, 1H), 8.56 (s, 1H). 13C NMR (100 MHz,
(125 MHz, DMSO-d6)
d 24.8 (t), 25.5 (t), 28.5 (t), 28.7 (t), 28.8 (t),
29.0 (t, 2C), 29.1 (t, 4C), 29.1 (t, 2C), 32.6 (t), 60.8 (t), 123.1 (d), 125.4
(d), 127.1 (d), 129.3 (s), 130.8 (d), 134.2 (d), 144.1 (s), 147.9 (s). Anal.
Calcd for C23H36N4O3: C, 66.32; H, 8.71; N,13.45. Found: C, 66.26; H,
8.77; N, 13.49.
CDCl3)
d 121.3 (s), 124.3 (d), 125.7 (d, 2C), 127.4 (s), 127.8 (d), 128.1
(s), 129.7 (d), 130.7 (d), 130.9 (d), 133.7 (d, 2C), 142.0 (s), 145.9 (s).
Anal. Calcd for C14H9BrN4O2: C, 48.72; H, 2.63; Br, 23.15; N, 16.23.
Found: C, 48.98; H, 2.39; Br, 23.19; N, 16.51.
4.3.17. 4,5-O-Isopropylidene-3-O-benzyl-1-deoxy-1-C-[(1-(2-
4.3.11. 4-(3-Bromophenyl)-1-(2-nitrophenyl)-1H-1,2,3-
nitrophenyl)-1H-1,2,3-triazol-4-yl)]-
D
-erythritol (3ak)
25
triazole (3ae)
Pale yellow oil. [
2885, 1720, 1609, 1588, 1537, 1506, 1454, 1355, 1214, 1071, 852, 748,
699 cmꢀ1. 1H NMR (200 MHz, CDCl3)
1.36 (s, 3H), 1.45 (s, 3H), 3.06
a
]
D
þ7.0 (c 3.5, CHCl3). IR (CHCl3):
n 3144, 2987,
Mp: 101 ꢁC. 1H NMR (400 MHz, CDCl3)
d
7.02–7.44 (m, 3H), 7.58–
7.82 (m, 4H), 7.94–8.04 (m, 2H). 13C NMR (100 MHz, CDCl3)
d
121.4
d
(d), 123.1 (s), 124.5 (d), 125.7 (d), 126.9 (d), 127.90 (d), 129.0 (d),
130.5 (d), 130.8 (d), 131.5 (d), 131.8 (s), 133.8 (s), 144.4 (s), 146.9 (s).
Anal. Calcd for C14H9BrN4O2: C, 48.72; H, 2.63; Br, 23.15; N, 16.23.
Found: C, 48.76; H, 2.52; Br, 23.42; N, 16.11.
(dd, J¼6.7, 15.2 Hz, 1H), 3.26 (dd, J¼4.1, 15.2 Hz, 1H), 3.86–3.94 (m,
2H), 4.02–4.17 (m, 2H), 4.61 (s, 2H), 7.24–7.31 (m, 5H), 7.54 (dd,
J¼1.6, 7.6 Hz, 1H), 7.65 (s, 1H), 7.67 (dt, J¼1.7, 7.7 Hz, 1H), 7.77 (dt,
J¼1.8, 7.7 Hz, 1H), 8.06 (dd, J¼1.7, 7.8 Hz, 1H). 13C NMR (50 MHz,
CDCl3) d 24.8 (q), 26.2 (q), 27.0 (t), 65.9 (t), 72.2 (t), 76.5 (d), 78.2 (d),
4.3.12. 4-(4-Bromophenyl)-1-(2-nitrophenyl)-1H-1,2,3-
108.8 (s), 123.5 (d), 125.0 (d), 127.0 (d), 127.2 (d), 127.4 (d, 2C), 127.9
(d, 2C), 129.6 (s), 130.2 (d), 133.4 (d), 137.7 (s), 143.9 (s), 144.2 (s).
Anal. Calcd for C22H24N4O5: C, 62.25; H, 5.70; N, 13.20. Found: C,
62.19; H, 5.67; N, 13.18.
triazole (3af)
Mp: 136–137 ꢁC. 1H NMR (400 MHz, CDCl3)
d
7.40–7.50 (m, 1H),
7.57 (dt, J¼2.2, 8.7 Hz, 1H), 7.65–7.88 (m, 5H), 8.06 (s, 1H), 8.06–8.22

3978
K.A. Dururgkar et al. / Tetrahedron 65 (2009) 3974–3979
4.3.18. (4R)-1,2-O-Isopropylidene-3-O-benzyl-4-C-[(1-(2-
nitrophenyl)-1H-1,2,3-triazol-4-yl)]- -threofuranose (3al)
þ5.6 (c 1.2, CHCl3). IR (CHCl3): 3018, 2923,
1725, 1609, 1539, 1508, 1454, 1355, 1076, 1026, 753, 666 cmꢀ1 1H
NMR (200 MHz, CDCl3)
(500 MHz, DMSO-d6) d 4.95 (s, 2H), 7.86–7.93 (m, 4H), 8.18 (d,
L
J¼9.1 Hz, 2H), 8.42 (d, J¼9.1 Hz, 2H), 9.00 (s, 1H). 13C (125 MHz,
25
Pale yellow oil. [
a]
n
DMSO-d6) d 32.9 (t), 120.6 (d, 2C), 121.8 (d), 123.3 (d, 2C), 125.6 (d,
D
.
2C), 131.7 (s, 2C), 134.6 (d, 2C), 140.8 (s), 144.4 (s), 146.7 (s), 167.4 (s,
2C). Anal. Calcd for C17H11N5O4: C, 58.45; H, 3.17; N, 20.05; Found:
C, 58.51; H, 3.21; N, 19.99.
d
1.37 (s, 3H), 1.58 (s, 3H), 4.23 (d, J¼3.0 Hz,
1H), 4.46 (dd, J¼12.0, 19.2 Hz, 2H), 4.75 (d, J¼3.7 Hz, 1H), 5.64 (d,
J¼3.0 Hz, 1H), 6.06 (d, J¼3.7 Hz, 1H), 7.14–7.19 (m, 2H), 7.24–7.30
(m, 3H), 7.46–7.51 (m, 1H), 7.65–7.81 (m, 2H), 7.96 (d, J¼0.6 Hz, 1H),
4.3.24. 2-(1-(4-Nitrophenyl)-1H-1,2,3-triazol-4-yl)propan-
8.07–8.11 (m, 1H). 13C NMR (50 MHz, CDCl3)
d
26.2 (q), 26.7 (q), 72.5
2-ol (3ch)
(t), 76.1 (d), 82.4 (d), 83.0 (d), 104.6 (d), 112.1 (s), 125.3 (d), 125.5 (d),
127.5 (d, 2C), 127.8 (d), 128.4 (d, 2C), 129.6 (d), 130.1 (s), 130.7 (d),
133.7 (d), 137.1 (s), 144.2 (s), 144.4 (s). Anal. Calcd for C22H22N4O6: C,
60.27; H, 5.06; N, 12.78. Found: C, 60.31; H, 5.12; N, 12.74.
Mp: 121–122 ꢁC. IR (Nujol):
n
3401, 3019, 2982, 1599, 1530, 1507,
1344, 1235, 1215, 1036, 855, 757, 668 cmꢀ1 1H NMR (500 MHz,
.
DMSO-d6)
d
1.54 (s, 6H), 5.34 (s, 1H), 8.23 (dd, J¼2.2, 7.1 Hz, 2H),
8.41 (dd, J¼2.2, 7.1 Hz, 2H), 8.81 (s, 1H). 13C NMR (125 MHz, DMSO-
d6) d 30.5 (q, 2C), 67.0 (s), 119.3 (d), 120.3 (d, 2C), 125.5 (d, 2C), 141.1
4.3.19. 1,2:4,5-Di-O-isopropylidene-3-O-[(1-(2-nitrophenyl)-1H-
(s), 146.5 (s), 157.6 (s). Anal. Calcd for C11H12N4O3: C, 53.22; H, 4.87;
N, 22.57. Found: C, 53.29; H, 4.93; N, 22.61.
1,2,3-triazol-4-yl)methyl]-
D
-fructopyranose (3am)
25
Pale yellow oil. [
2935, 2400,1734, 1609, 1541, 1508, 1457, 1382, 1218, 1117, 1082, 1017,
882, 768, 668 cmꢀ1. 1H NMR (200 MHz, CDCl3)
1.39 (s, 6H), 1.49 (s,
a]
ꢀ62.23 (c 1.0, CHCl3). IR (CHCl3):
n
3018,
Crystal data for 3ch (C11H12N4O3): M¼248.25, crystal di-
D
mensions 0.30ꢂ0.12ꢂ0.06 mm3, monoclinic, space group P21/c,
d
a¼13.948(4),
b¼12.875(4),
c¼6.5711(18) Å,
b
¼93.463(5)ꢁ,
3H),1.59 (s, 3H), 3.62 (d, J¼7.3 Hz,1H), 3.92 (d, J¼8.59 Hz,1H), 4.05–
4.14 (m, 3H), 4.23 (dd, J¼1.9, 5.6 Hz, 1H), 4.39 (dd, J¼5.9, 7.2 Hz, 1H),
4.94 (d, J¼12.7 Hz, 1H), 5.17 (d, J¼12.7 Hz, 1H), 7.62 (dd, J¼1.4,
7.6 Hz, 1H), 7.72 (dd, J¼1.6, 7.8 Hz, 1H), 7.78 (dd, J¼1.7, 7.5 Hz, 1H),
7.86 (s, 1H), 8.08 (dd, J¼1.6, 7.8 Hz, 1H). 13C NMR (50 MHz, CDCl3)
V¼1177.9(6) Å3, Z¼4; rcalcd¼1.400 g cmꢀ3
,
m
(Mo K
a
)¼0.105 mmꢀ1
,
F(000)¼520, T¼133(2) K, 2qmax¼51.00ꢁ, 8641 reflections collected,
2183 unique, 1969 observed (I>2s(I)) reflections, 211 refined pa-
rameters,
R
value 0.0599, wR2¼0.1505 (all data R¼0.0651,
wR2¼0.1526), S¼1.155, minimum and maximum transmission
d
25.5 (q), 25.8 (q), 26.4 (q), 27.8 (q), 59.7 (t), 64.2 (t), 71.3 (t), 73.4
0.9691 and 0.9937, respectively, maximum and minimum residual
(d), 76.2 (d), 77.0 (d), 103.8 (s), 108.7 (s), 111.6 (s), 123.8 (d), 125.1 (d),
127.2 (d), 129.5 (s), 130.5 (d), 133.6 (d), 144.0 (s), 145.4 (s). Anal.
Calcd for C21H26N4O8: C, 60.39; H, 7.43. Found: C, 60.44; H, 7.39.
electron densities þ0.353 and ꢀ0.224 e Åꢀ3
.
4.3.25. 2-(1-(4-Nitrophenyl)-1H-1,2,3-triazol-4-yl)ethanol23 (3ci)
Mp: 148–150 ꢁC. IR (CHCl3):
3311, 1596, 1528, 1502, 1462, 1376,
1340, 1242, 1045, 853 cmꢀ1. 1H NMR (500 MHz, DMSO-d6)
2.87 (t,
n
4.3.20. 4-(2-Bromophenyl)-1-(4-nitrophenyl)-1H-1,2,3-
d
triazole (3cd)
J¼6.8 Hz, 2H), 3.70–3.74 (m, 2H), 4.81 (t, J¼5.4 Hz,1H), 7.14–7.18 (m,
Mp: 170–171 ꢁC. 1H NMR (400 MHz, CDCl3)
d
7.26 (ddd, J¼1.8,
2H), 8.38–8.41 (m, 2H), 8.75 (s, 1H). 13C NMR (125 MHz, DMSO-d6)
7.4, 9.2 Hz, 1H), 7.47 (dt, J¼1.2, 7.8 Hz, 1H), 7.69 (dd, J¼1.2, 7.9 Hz,
1H), 8.04 (t, J¼2.6 Hz, 1H), 8.09 (t, J¼2.6 Hz, 1H), 8.2 (dd, J¼1.6,
7.8 Hz, 1H), 8.42 (t, J¼2.6 Hz, 1H), 8.47 (t, J¼2.6 Hz, 1H), 8.79 (s, 1H).
d 29.1 (t), 60.1 (t), 120.2 (d, 2C), 121.2 (d), 125.6 (d, 2C), 141.0 (s),
146.4 (s), 146.5 (s). Anal. Calcd for C10H10N4O3: C, 51.28; H, 4.30; N,
23.92. Found: C, 51.34; H, 4.26; N, 23.87.
13C NMR (100 MHz, CDCl3)
d 120.5 (d), 121.3 (s), 124.1 (d), 124.9 (d),
125.6 (d), 127.9 (d), 130.0 (d), 130.2 (d), 130.8 (d), 131.9 (s), 133.8 (d),
141.1 (s), 146.7 (s), 147.3 (s). Anal. Calcd for C14H9BrN4O2: C, 48.72;
H, 2.63; Br, 23.15; N, 16.23. Found: C, 48.57; H, 2.90; Br, 22.89; N,
16.12.
4.3.26. 1,2:4,5-Di-O-isopropylidene-3-O-[(1-(4-nitrophenyl)-1H-
1,2,3-triazol-4-yl)methyl]-
Mp: 135–137 ꢁC. IR (CHCl3):
1508, 1382, 1342, 1218, 1118, 1082, 854, 751 cmꢀ1
(500 MHz, CDCl3) 1.39 (s, 3H), 1.41 (s, 3H), 1.50 (s, 3H), 1.57 (s, 3H),
D
-fructopyranose (3cm)
3400, 2990, 2935, 1599, 1528,
1H NMR
n
.
d
4.3.21. 4-(3-Bromophenyl)-1-(4-nitrophenyl)-1H-1,2,3-
3.63 (d, J¼7.6 Hz, 1H), 3.96 (d, J¼8.6 Hz, 1H), 4.04 (d, J¼13.4 Hz, 1H),
4.12–4.17 (m, 2H), 4.25 (dd, J¼2.2, 5.6 Hz, 1H), 4.39 (dd, J¼5.6,
7.1 Hz, 1H), 4.92 (d, J¼12.5 Hz, 1H), 5.17 (d, J¼12.7 Hz, 1H), 7.98 (dd,
J¼2.0, 7.1 Hz, 2H), 8.14 (s, 1H), 8.42–8.45 (m, 2H). 13C NMR
triazole (3ce)
Mp: 217–218 ꢁC. 1H NMR (400 MHz, DMSO-d6)
d
7.36–7.54 (m,
2H), 7.96 (dt, J¼1.8, 7.6 Hz, 1H), 8.14 (t, J¼1.6 Hz,1H), 8.26, 8.31, 8.45,
8.51 (4br m, 4H), 9.47 (s, 1H). 13C NMR (100 MHz, DMSO-d6)
118.6
d
(125 MHz, CDCl3) d 26.1 (q), 26.2 (q), 26.6 (q), 28.2 (q), 60.2 (t), 65.1
(d, 2C), 120.8 (d), 122.6 (s), 123.8 (d), 124.1 (d), 126.5 (d), 127.4 (d),
129.1 (d),129.4 (d),130.5 (s),139.3 (s),145.0 (s),145.1 (s). Anal. Calcd
for C14H9BrN4O2: C, 48.72; H, 2.63; Br, 23.15; N, 16.23. Found: C,
48.63; H, 2.88; Br, 23.29; N, 16.48.
(t), 71.9 (t), 73.8 (d), 77.3 (d), 77.4 (d), 104.2 (s), 109.2 (s), 112.1 (s),
120.3 (d, 2C), 120.4 (d), 125.5 (d, 2C), 141.1 (s), 147.1 (s), 147.2 (s).
Anal. Calcd for C21H26N4O8: C, 54.54; H, 5.67; N, 12.12. Found: C,
54.60; H, 5.71; N, 12.18.
4.3.22. 4-(4-Bromophenyl)-1-(4-nitrophenyl)-1H-1,2,3-
Acknowledgements
triazole (3cf)
Mp: 149–150 ꢁC. 1H NMR (400 MHz, DMSO-d6)
d 7.59 (t,
We thank Ministry of Science Technology for funding through
the Department of Science and Technology under Green Chemistry
Program (No. SR/S5/GC-20/2007). Financial support from CSIR
(New Delhi) in the form of a research fellowship to K.A.D. is
gratefully acknowledged.
J¼2.2 Hz, 1H), 7.64 (t, J¼2.2 Hz, 1H), 7.77 (t, J¼2.2 Hz, 1H), 7.82
(t, J¼2.2 Hz, 1H), 8.01 (t, J¼2.2 Hz, 1H), 8.06 (t, J¼2.2 Hz, 1H), 8.28 (t,
J¼2.2 Hz, 1H), 8.44 (t, J¼2.2 Hz, 1H), 8.48 (t, J¼2.2 Hz, 1H). 13C NMR
(100 MHz, DMSO-d6) d 118.2 (d),118.5 (d, 2C),119.9 (s),123.7 (d, 2C),
125.5 (d, 2C), 127.3 (s), 130.1 (d, 2C), 139.1 (s), 144.9 (s), 145.2 (s).
Anal. Calcd for C14H9BrN4O2: C, 48.72; H, 2.63; Br, 23.15; N, 16.23.
Found: C, 48.70; H, 2.40; Br, 23.43; N, 16.01.
References and notes
1. (a) Smith, M. B.; March, J. Advanced Organic Chemistry, 5th ed.; Wiley-Inter-
science: New York, NY, 2001; Chapter 13, p 850; (b) Terrier, F. Nucleophilic Ar-
omatic Displacement; VCH: New York, NY, 1991; (c) Paradisi, C. Comprehensive
Organic Synthesis; Pergamon: Oxford, 1991; Vol. 4, pp 423–450; (d) Buncel, E.;
Dust, J. M.; Terrier, F. Chem. Rev. 1995, 95, 2261–2280; (e) Zoltewics, J. A. Top.
4.3.23. 2-((1-(4-Nitrophenyl)-1H-1,2,3-triazol-4-yl)methyl)-
isoindoline-1,3-dione (3cg)
Mp: 266–268 ꢁC. IR (CHCl3):
n
3129, 2725, 1764, 1717, 1594, 1520,
1503, 1455, 1338, 1246, 1043, 935, 857, 773, 718 cmꢀ1 1H NMR
.

K.A. Dururgkar et al. / Tetrahedron 65 (2009) 3974–3979
3979
Curr. Chem. 1975, 59, 33–64; (f) Bunnett, J. F.; Zahler, R. E. Chem. Rev. 1951, 49,
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9. For in situ aryl azides synthesis and their [3þ2] cycloaddition reaction in one
pot, see: (a) Feldman, A. K.; Colasson, B.; Fokin, V. V. Org. Lett. 2004, 6, 3897–
3899; (b) Andersen, J.; Bolvig, S.; Liang, X. Synlett 2005, 2941–2947; (c) Barral,
K.; Moorhouse, A. D.; Moses, J. E. Org. Lett. 2007, 9, 1809–1811; (d) Beckmann,
H. S. G.; Wittmann, V. Org. Lett. 2007, 9, 1–4; (e) Tao, C.-Z.; Cui, X.; Li, J.; Liu,
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u
and
f
scan mode, lMo ¼0.71073 Å.
K
a
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