Iron-catalyzed C-C bond cleavage and C-N bond formation

Article abstract of DOI:10.1002/adsc.201200324

A novel approach for C-N bond formation was developed by iron-catalyzed C-C bond cleavage. Anilines and sulfonamides reacted smoothly with 2-substituted 1,3-diphenylpropane-1,3-diones to afford N-alkylation products, in which the 1,3-dicarbonyl group acts as a leaving group in the presence of an iron catalyst. The reversible C-C bond cleavage plays a driving force to give the thermodynamically stable products. The method is complementary to the previous methods for C-N bond formation. Copyright

Full text of DOI:10.1002/adsc.201200324

FULL PAPERS
DOI: 10.1002/adsc.201200324
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Iron-Catalyzed C C Bond Cleavage and C N Bond Formation
Wenjuan Li,a Xiaojian Zheng,a and Zhiping Lia,*
a
Department of Chemistry, Renmin University of China, Beijing 100872, Peopleꢀs Republic of China
Fax : (+86) 10-6251-6444; e-mail: zhipingli@ruc.edu.cn
Received: April 17, 2012; Revised: October 18, 2012; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201200324.
À
Abstract: A novel approach for C N bond formation plays a driving force to give the thermodynamically
À
was developed by iron-catalyzed C C bond cleavage. stable products. The method is complementary to the
Anilines and sulfonamides reacted smoothly with 2- previous methods for C N bond formation.
À
substituted 1,3-diphenylpropane-1,3-diones to afford
N-alkylation products, in which the 1,3-dicarbonyl Keywords: amination; C C bond activation; C N
À
À
group acts as a leaving group in the presence of an bond formation; iron catalysis; nucleophilic substitu-
À
iron catalyst. The reversible C C bond cleavage tion
Introduction
compounds,[14] we also found that the oxidative cou-
pling reaction was reversible. We recently reported
À
C C bond activation is one of great challenges in or- Friedel–Crafts alkylation and cyclization based on
ganic chemistry.[1] A major reason is attributed to the iron-catalyzed C C bond cleavage, in which the 1,3-
À
fact that C C bond cleavage is thermodynamically dicarbonyl acted as a new leaving group.[15]
À
À
much less favored than C C bond formation. Three
N-Alkylation of amines is typically achieved by the
À
general strategies for C C bond cleavage have been reactions of amines with halides or organometallic re-
investigated extensively, including the energy release agents.[16] The advantages of these methods are some-
of strained molecules,[2] the cleavage an a-C C bond how offset by the toxic nature of halogens or the use
À
to a carbonyl,[3] cyano,[4] carboxylic acid[5] or hydroxy of stoichiometric metal reagents. The use of alcohols
group[6] and chelation assistance.[7] However, the is therefore potentially an excellent alternative
À
linear Csp3
C
sp3 bond activation is far under-developed method for the alkylation of amines.[17] However, the
because of the lack of a driving force to cleave the poor electrophilicity of most alcohols limits their ap-
[8]
À
unstrained C C bond. In 2004, Kotora and co-work- plication, especially for the electron-deficient amines
ers reported the catalytic deallylation of malonates and amides. Therefore, finding alternative methods
À
via selective cleavage of the C C bond between 1,3- for alkylation of the weak nucleophilic amines and
dicarbonyl and allyl groups.[9] A quaternary carbon is amides is highly attractive.[18] Here we report a novel
À
À
essential for this process and enolization of the car- C C bond cleavage/C N bond formation reaction as
bonyl is proposed to promote the cleavage of the allyl an efficient route to N-alkylation products by the use
group. Fillion and co-workers firstly disclosed an effi- of a 1,3-dicarbonyl as leaving group (Scheme 1). The
cient and selective method for the hydrogenolysis of present method uses electron-deficient amines and
À
benzyl-Meldrumꢀs acids through Pd-catalyzed cleav- amides and offers a new complementary route to C
age of an unstrained Csp3 Csp3 bond.[10] Zhai and Ye N bond formation under mild reaction conditions.
À
also reported an excellent SmI2-promoted reductive
À
C C bond fragmentation reaction of a-aminomethyl
malonates.[11] In 2005, Li and Yao observed the cleav-
À
age of a C C bond between 1,3-dicarbonyl and
benzyl groups in the Ag-catalyzed addition of activat-
ed methylene compounds to styrenes.[12] The results
suggested that the formation of the thermodynamical-
À
ly stable product drove the reversible C C bond for-
mation to completion.[13] In the course of our studies
À
À
À
on benzyl C H oxidative coupling with 1,3-dicarbonyl Scheme 1. C C bond cleavage and C N bond formation.
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Results and Discussion
decreased the reactivity to give 3a only in 16% yield
(entry 17). Importantly, the desired product 3a could
Initially, the reaction of 2-benzhydryl-1,3-diphenylpro- not be obtained in the absence of an iron catalyst
pane-1,3-dione 1a with 4-nitroaniline 2a was studied (entry 18).
as a model reaction to examine the suitable reaction
Having the optimized conditions in hand, we subse-
conditions (Table 1). Catalyst screening experiments quently investigated the scope of amines by the use of
with various iron sources (entries 1–5) as well as some 1a as the model substrate. As shown by the results in
other metal salts (entries 6–11) indicated that non-ex- Table 2, a variety of anilines and sulfonamides 2 could
pensive and moisture stable FeCl3·6H2O was the best be applied for the present transformation. Anilines
catalyst, which gave N-benzhydryl-4-nitroaniline 3a in with electron-withdrawing groups reacted with 1a
a moderate yield (47%, entry 2). To our delight, the more efficiently, produced the corresponding com-
À
C N bond forming reaction could be achieved in pounds 3a–c with good yields (entries 1–3). Only
higher yields by increasing the amount of 4-nitroani- moderate yields could be obtained when electron-do-
line (entries 12 and 13). An excellent result was ob- nating substituted anilines were used in this reaction
tained using 5 equivalents of 2a in DCE at 1008C (entries 4 and 5). However, aniline 2f led to a low
(91%, entry 13). It is worth noting that the in situ gen- yield of 3f even in the presence of 20 mol%
erated 1,3-diphenylpropane-1,3-dione and the remain- FeCl3·6H2O (entry 6). Anilines 2g–h with polysub-
ing 2a were quantitatively isolated after the reaction stituents could also gave the N-alkylation products,
work-up. The results suggested that the condensation while the yields of the desired products were not sat-
À
of 1a with 2a was unlikely attributed to C C bond isfactory (entries 7 and 8). Sulfonamides 2i and 2j
cleavage. Moreover, other solvents, such as THF,
DMF, and MeCN (entries 14–16), were totally ineffec-
tive for this transformation. In comparison, CH2Cl2
Table 2. The reactions of 1a with anilines and amides.[a]
Table 1. Optimization of the reaction conditions.[a]
Entry
R
2/3
Yield [%][b]
1
2a/3a
2b/3b
2c/3c
2d/3d
2e/3e
2f/3f
90
83
66
53
55
31
Entry 2a (equiv.) Catalyst
Solvent Yield [%][b]
2
1
2
3
4
5
6
7
8
1
1
1
1
1
1
1
1
1
1
1
3
5
5
5
5
5
5
FeCl3
FeCl3·6H2O
FeCl2
Fe2(CO)9
FeACTHNGURETNNU(G OAc)2
CuBr
CuCl2·2H2O
AlCl3
ZnCl2
CoCl2·6H2O
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
46
47
28
3
4[c]
5[c]
6[c]
[c]
N.D.[d]
N.D.[d]
N.D.[d]
16
N.D.[d]
N.D.[d]
N.D.[d]
34
9
10
11
12
13
14[e]
15
16
17[f]
18
7
2g/3g
2h/3h
29
HAuCl4·4H2O DCE
FeCl3·6H2O
FeCl3·6H2O
FeCl3·6H2O
FeCl3·6H2O
FeCl3·6H2O
FeCl3·6H2O
–
DCE
DCE
THF
DMF
MeCN
65
91
N.D.[d]
N.D.[d]
<5
8
9
58
70
CH2Cl2 16
DCE
2i/3i
2j/3j
N.D.[d]
[a]
Reaction conditions: 1a (0.2 mmol), cat. (0.02 mmol), sol-
vent (2.0 mL), 1008C, 12 h, N2.
10[c]
69
[b]
[c]
[d]
[e]
[f]
NMR yields based on 1a, using an internal standard.
0.01 mmol
[a]
Reaction conditions: 1a (0.2 mmol),
FeCl3·6H2O (0.02 mmol), DCE (2.0 mL).
Isolated yields.
2
(1.0 mmol),
1
N.D.: not detected by H NMR.
[b]
[c]
808C.
508C.
FeCl3·6H2O (0.04 mmol).
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Iron-Catalyzed C C Bond Cleavage and C N Bond Formation
Table 3. The reactions of 1 with 2.[a]
Entry
1
2
Product
3
Yield [%][b]
2a
3k
85
2
3
2i
2j
3l
74
67
3m
Scheme 2. Alkylation of electron-deficient anilines.
4
5
2a
2a
3n
3o
74
65
were both applicable to this transformation, leading
to the corresponding products in 70% and 69%
yields, respectively (entries 9 and 10). The application
of acetylamides failed to give the corresponding prod-
ucts. These results indicated that the efficiency of the
present C N bond formation reaction would be af-
fected by both the acidity and nucleophilicity of the
nitrogen sources.
À
Interestingly, the Friedel–Crafts alkylation products
4–6 were selectively obtained with 79%, 87%, and
94% yields, respectively, when dione 1a reacted with
tetrafluoroaniline 2k, 2-nitroaniline 2l, and 2,6-di-
chloroaniline 2m under the optimized reaction condi-
tions, while the expected N-alkylation product was
not observed (Scheme 2). The results are consistent
with our previous results on the Friedel–Crafts-type
reaction under essentially the same conditions.[15]
Therefore, we concluded that the para-substituted
Friedel–Crafts products are preferentially generated
in the cases of anilines with ortho-substituent(s). Al-
ternatively, this highly selective transformation pro-
vides a convenient approach to the alkylation of elec-
6[c]
2d
2a
2a
3p
3q
3r
42
70
51
7
8[c]
À
tron-deficient arenes through C C bond cleavage,
which is difficult to achieve by the reported meth-
ods.[19]
9[c]
2g
2i
3s
3t
53
75
Furthermore, the scope of the 1,3-diones 1 was also
À
investigated for the present iron-catalyzed C N bond
formation (Table 3). Diones with halo-substituted
aryls reacted with 4-nitroaniline 2a smoothly, produc-
ing the desired products 3k–n (entries 1–4). Although
an electron-donating substituent on the phenyl ring of
the dione decreased the efficiency of the transforma-
tion slightly (entry 5), electron-rich aniline 2d showed
10[c]
À
lower activity in this C N bond forming reaction
(entry 6). An allyl 1,3-dicarbonyl substrate was also
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1,2-dihydronaphthalene 9, was isolated as the major
product [Eq. (1)]. This is dramatically different from
our result of entry 11 in Table 3. These results indicat-
Table 3. (Continued)
Entry
11
2
Product
3
Yield [%][b]
2a
3u
61
12
2b
2a
3v
45 (62)[d]
ed that the current approach using 1,3-dicarbonyl as
a leaving group would be an excellent alternative
À
method for C N bond formation.
In the course of our investigation of the scope of
the present transformation, we found that the ring-
opening product 10 was obtained as the major prod-
uct by the reaction of the cyclopropyl substrate 1i
with 2a under the standard reaction conditions [Eq.
13
3w
47 (53)[d]
[a]
Reaction conditions:
FeCl3·6H2O (0.02 mmol), DCE (2.0 mL).
Isolated yields.
FeCl3·6H2O (0.04 mmol).
Anilines (1.6 mmol).
1
(0.2 mmol),
2
(1.0 mmol),
À
(2)], while the C N coupling product 3x was the
[b]
[c]
[d]
major product at room temperature [Eq. (3)]. Subse-
quently, the transformation of 3x into 10 was proven
by the reaction of 3x with 2a at 1008C in the presence
of the iron catalyst [Eq. (4)]. These results indicated
that 3x is the kinetic product and 10 is the thermody-
compatible, and the product 3q was obtained in 70% namic product in the reaction of 1i and 2a [Eq. (2)].
yield (entry 7) under the optimized reaction condi- In addition, the conversion of 3b into 1a further sup-
tions.[20] The reactions also proceeded with methyl- ports that the cleavage and formation of C C bond
substituted 1,3-dicarbonyl substrates (entries 8–10). and C N bond are reversible and drives the equi-
À
[21]
À
However, in these cases, increasing the catalyst load- librium to the thermodynamically stable product [Eq.
À
ing is necessary to keep the efficiency of C N bond (5)].
formation. To our delight, hexa- or pentacyclic sub-
To investigate the possible pathways of the present
À
strates reacted with various anilines all affording the C C bond cleavage, we performed radical trapping
corresponding products with moderate yields (en- experiments (Scheme 4).[22] The present transforma-
tries 11–13).
tion was suppressed by adding TEMPO (entry 1) and
To demonstrate that our substitution protocol is galvinoxyl (entry 2) to some exent, however, 2,6-di-
À
complementary to the existing C N bond formation tert-butyl-4-methylphenol (BHT) showed no effect on
reactions,[16,17] a series of comparative experiments the reactions (entry 3). Taking into account these re-
was carried out under the optimized reaction condi- sults, we rationalized that possible FeCl3-TEMPO ad-
tions. As shown in Scheme 3, using diphenylmethanol ducts (a possible one is shown in Figure 1) were
À
7 as the alkylation reagent, the corresponding prod- formed in situ and deactivated the present C C bond
ucts were obtained in substantially lower yields, com- cleavage.[23,24] To confirm our hypothesis, TEMPO
À
paring with the present C C bond cleavage method. (20 mol%) and FeCl3 (10 mol%) were premixed in
Noticeably, the reaction of 1,2,3,4-tetrahydronaphtha- DCE at 1008C for 1 hour, then 1a and 2a were added
len-1-ol
8
with 4-nitroaniline 2a catalyzed by into the reaction mixture [Eq. (6)]. The expected
FeCl3·6H2O in DCE gave the corresponding product product 3a was indeed formed in only a trace amount
3u merely in 8% yield, and the dehydrated product, (<5%). Importantly, the premixed catalysts led to 3x
rather that 10 [Eq. (7)], which indicated that the reac-
tion most likely proceeds through an ionic mecha-
nism.[25]
Moreover, in order to assess the nature of charge
development in the transition state of the reaction,
a Hammett study[26] was conducted on the relative re-
activity of substituted substrates [Eq. (8)]. The bond-
ing plot (Figure 2) illustrates the change of the rate-
limiting step during reaction of different substrates,
Scheme 3. Alcohol as an alkylation reagent.
and the slope of the line involving the electron-with-
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Iron-Catalyzed C C Bond Cleavage and C N Bond Formation
Scheme 4. Radical trapping experiments.
Figure 1. A possible structure of FeCl3-TEMPO.
drawing groups (R=F, Cl) yields a 1 value of À1.8,
À
thus indicating an electrophilic nature of the C C
À
bond cleavage and C N bond formation reaction (see
details in the Supporting Information).[27]
On the basis of these experimental results, a possi-
À
ble mechanism for the iron-catalyzed C N bond for-
mation is shown in Scheme 5. The coordination of
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pane-1,3-dione was released simultaneously. This
inner sphere model could partially explain why 3u
was formed in 61% yield (Table 3, entry 11), while
only 8% yield was obtained using alcohol as the alky-
lation reagent [Eq. (1)].
Conclusions
In conclusion, we have developed a novel approach
À
À
for C N bond formation via iron-catalyzed C C bond
cleavage under mild reaction conditions. The method
is complementary to the traditional N-alkylation and
is highlighted by its efficiency, selectivity and generali-
À
ty. The reversible C C bond cleavage plays a driving
force to give the thermodynamically stable products.
The scope, mechanism, and synthetic applications are
under investigation.
Figure 2. Hammett plot of logACHTNUGRTNEUNG
(KX/KH) vs Ss+.
Experimental Section
General Comments
All reactions were carried out under an N2 atmos-
phere using a standard Schlenk tube techniques. Sol-
vents were distilled from appropriate drying agents
prior to use. All reagents were purchased from Alfa,
Acros, Aldrich or TCI, and used without further pu-
rification. Flash chromatography was performed on
silca gel (silca gel, 200–300 mesh). 1H NMR and
13C NMR spectra were recorded on Bruker 400 MHz
and Bruker 100 MHz spectrometers with CDCl3 as
the solvent. Mass spectra were determined with AEI-
MS 50 for EI-MS, APEX (II) (Bruker Inc.) for HR-
MS and ESI-MS. IR spectra were recorded by an IR
Prestige-21 (Shimadzu) infrared spectrometer.
General Procedure for the Synthesis of Compounds
3, 4–6 and 10
Scheme 5. A proposed reaction mechanism.
To a dry Schlenk tube filled with nitrogen, a mixture of
FeCl3·6H2O (0.02 mmol), 1 (0.2 mmol), and 2 (1.0 mmol),
were added at room temperature, then freshly distilled 1,2-
dichloroethane (2.0 mL) was injected through a syringe. The
reaction mixture was stirred at 1008C for 12 h. Then the re-
sulting solution was cooled to room temperature, and sol-
iron catalyst to 1,3-dicarbonyl gives a p-complex A,[28]
which leads to the reversible C C bond cleavage.
This ion-pair generated in situ was trapped by anilines
[29]
À
to give the N-alkylation product, and 1,3-diphenylpro- vent was evaporated under vacuum, the residue was purified
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Iron-Catalyzed C C Bond Cleavage and C N Bond Formation
by flash column chromatography on silica gel (eluent: ethyl
acetate/petroleum ether) to give the desired product.
N-Benzhydryl-4-nitroaniline (3a):[30] Isolated by flash
column chromatography (ethyl acetate/petroleum ether=
2-(Benzhydrylamino)-4,5-dimethoxybenzonitrile (3h): Iso-
lated by flash column chromatography (ethyl acetate/petro-
1
leum ether=1:10, Rf =0.4). H NMR: d=7.38–7.32 (m, 8H),
7.30–7.26 (m, 2H), 6.84 (s, 1H), 6.01 (s, 1H), 5.56 (d, J=
4.4 Hz, 1H), 4.92 (d, J=4.4 Hz, 1H), 3.77 (s, 3H), 3.55 (s,
3H); 13C NMR: d=154.4, 146.3, 141.5, 140.9, 129.0, 127.9,
127.2, 118.3, 114.3, 97.1, 86.0, 63.1, 56.5, 55.5; ATR-FTIR:
n=2950, 2916, 2849, 2357, 2204, 1617, 1521, 1456, 1412,
1222, 1066, 832, 741 cmÀ1; MS (EI): m/z (%)=344 (M), 167,
105, 77, 57, 43, 28 (100), 26; HR-MS (ESI): m/z=343.1443,
calcd. for C22H19N2O2 (M+): 343.1441.
1
1:10, Rf =0.4). H NMR: d=8.02 (d, J=9.2 Hz, 2H), 7.38–
7.28 (m, 10H), 6.50 (d, J=9.2 Hz, 2H), 5.63 (d, J=4.8 Hz,
1H), 5.01 (d, J=4.0 Hz, 1H); 13C NMR: d=152.0, 141.0,
138.5, 129.0, 128.0, 127.3, 126.2, 112.1, 62.4.
4-(Benzhydrylamino)benzonitrile (3b):[31] Isolated by flash
column chromatography (ethyl acetate/petroleum ether=
1
1:10, Rf =0.5). H NMR: d=7.36–7.26 (m, 12H), 6.51 (d, J=
N-Benzhydryl-4-methylbenzenesulfonamide (3i):[34] Isolat-
ed by flash column chromatography (dichloromethane/pe-
troleum ether=1:1, Rf =0.2). 1H NMR: d=7.54 (d, J=
8.4 Hz, 2H), 7.21–7.17 (m, 6H), 7.11–7.08 (m, 6H), 5.56 (d,
J=7.6 Hz, 1H), 5.46 (s, 1H), 2.35 (s, 3H); 13C NMR: d=
143.1, 140.5, 137.3, 129.3, 128.5, 127.5, 127.3, 127.1, 61.3,
21.4.
8.8 Hz, 2H), 5.55 (d, J=4.8 Hz, 1H), 4.76 (d, J=4.0 Hz,
1H); 13C NMR: d=150.1, 141.3, 133.5, 128.9, 127.8, 127.3,
120.2, 113.1, 99.4, 62.3.
N-Benzhydryl-4-bromoaniline (3c): Isolated by flash
column chromatography (ethyl acetate/petroleum ether=
1
1:20, Rf =0.5). H NMR: d=7.32–7.22 (m, 10H), 7.16 (d, J=
8.8 Hz, 2H), 6.39 (d, J=8.8 Hz, 2H), 5.44 (d, J=3.2 Hz,
1H), 4.25 (s, 1H); 13C NMR: d=146.2, 142.3, 131.8, 128.8,
127.5, 127.4, 115.0, 109.3, 62.9; ATR-FTIR: n=3412, 3082,
3059, 3026, 2922, 2851, 1593, 1491, 1450, 1395, 1292, 1236,
N-Benzhydrylmethanesulfonamide (3j):[32] Isolated by
flash column chromatography (dichloromethane/petroleum
1
ether=1:1, Rf =0.3). H NMR: d=7.37–7.25 (m, 10H), 5.75
1178, 1122, 1074, 1062, 1028, 999, 812, 758, 700, 503 cmÀ1
;
(d, J=7.6 Hz, 1H), 5.35 (d, J=7.6 Hz, 1H), 2.64 (s, 3H);
13C NMR: d=140.6, 128.9, 128.0, 127.4, 61.2, 41.9.
MS (EI): m/z (%)=337 (M), 260, 167 (100), 152, 128, 91,
77, 51, 39; HR-MS (ESI): m/z=336.0380, calcd. for
C19H15BrN (M+): 336.:0382.
N-((4-Chlorophenyl)ACTHNUGRTENUNG(phenyl)methyl)-4-nitroaniline
(3k):[34] Isolated by flash column chromatography (ethyl ace-
1
tate/petroleum ether=1:10, Rf =0.5). H NMR: d=7.98 (d,
N-Benzhydryl-4-methylaniline (3d):[32] Isolated by flash
column chromatography (ethyl acetate/petroleum ether=
1:30, Rf =0.7). 1H NMR: d=7.34–7.29 (m, 8H), 7.26–7.21
(m, 2H), 6.92 (d, J=8.4 Hz, 2H), 6.46 (d, J=8.4 Hz, 2H),
5.46 (s, 1H), 4.10 (s, 1H), 2.20 (s, 3H); 13C NMR: d=145.2,
143.2, 129.6, 128.7, 127.5, 127.3, 126.9, 113.6, 63.3, 20.4.
N-Benzhydryl-4-benzylaniline (3e): Isolated by flash
column chromatography (ethyl acetate/petroleum ether=
1:20, Rf =0.7). 1H NMR: d=7.33–7.28 (m, 8H), 7.26–7.22
(m, 4H), 7.16–7.14 (m, 3H), 6.92 (d, J=8.4 Hz, 2H), 6.47
(d, J=8.4 Hz, 2H), 5.44 (s, 1H), 4.15 (s, 1H), 3.83 (s, 2H);
13C NMR: d=145.7, 143.1, 141.9, 130.3, 129.5, 128.9, 128.8,
128.4, 127.4, 127.3, 125.8, 113.6, 63.3, 41.1; ATR-FTIR: n=
3400, 2925, 2918, 2850, 2359, 2342, 1615, 1515, 1493, 1452,
1313, 1183, 1089, 836, 792, 744 cmÀ1; MS (EI): m/z (%)=
349 (M), 182, 167 (100), 152, 128, 105, 91, 77, 61, 43, 28;
HR-MS (ESI): m/z=348.1742, calcd. for C26H22N (M+):
348.1747.
J=9.2 Hz, 2H), 7.37–7.24 (m, 9H), 6.49 (d, J=9.2 Hz, 2H),
5.60 (d, J=4.8 Hz, 1H), 5.08 (s, 1H); 13C NMR: d=151.9,
140.6, 139.4, 138.5, 133.7, 129.1, 128.6, 128.2, 127.3, 126.1,
112.1, 61.7.
N-[(4-Chlorophenyl)ACTHNUTRGNE(NUG phenyl)methyl]-4-methylbenzenesul-
fonamide(3l):[35] Isolated by flash column chromatography
1
(dichloromethane/petroleum ether=1:1, Rf =0.3). H NMR:
d=7.53 (d, J=8.0 Hz, 2H), 7.19–7.04 (m, 11H), 5.72 (s,
1H), 5.52 (d, J=7.6 Hz, 1H), 2.37 (s, 3H); 13C NMR: d=
143.3, 140.0, 139.0, 137.1, 133.3, 129.3, 128.7, 128.6, 128.5,
127.7, 127.2, 127.1, 60.7, 21.4.
N-[(4-Chlorophenyl)ACHTUNRGTNE(NUG phenyl)methyl]methanesulfonamide
(3m):[36] Isolated by flash column chromatography (dichloro-
1
methane/petroleum ether=1:1, Rf =0.3). H NMR: d=7.39–
7.25 (m, 9H), 5.72 (d, J=7.6 Hz, 1H), 5.34 (d, J=7.6 Hz,
1H), 2.67 (s, 3H); 13C NMR: d=140.2, 139.2, 133.8, 129.0,
128.9, 128.7, 128.2, 127.3, 60.6, 41.9.
N-[Bis(4-fluorophenyl)methyl]-4-nitroaniline (3n): Isolat-
ed by flash column chromatography (dichloromethane/ethyl
N-Benzhydrylaniline (3f):[33] Isolated by flash column
chromatography (ethyl acetate/petroleum ether=1:30, Rf =
0.7). 1H NMR: d=7.37–7.30 (m, 9H), 7.26–7.23 (m, 2H),
7.11 (dd, J=8.4, 7.6 Hz, 2H), 6.69 (t, J=7.2 Hz, 1H), 6.53
(d, J=8.0 Hz, 2H), 5.49 (s, 1H), 4.22 (s, 1H); 13C NMR: d=
147.4, 143.0, 129.1, 128.8, 127.5, 127.4, 117.7, 113.5, 63.1.
N-Benzhydryl-2,4-dinitroaniline (3g): Isolated by flash
column chromatography (ethyl acetate/petroleum ether=
1
ether/petroleum ether=3:2:15, Rf =0.4). H NMR: d=8.01
(d, J=9.2 Hz, 2H), 7.29–7.24 (m, 4H), 7.07–7.01 (m, 4H),
6.50 (d, J=9.2 Hz, 2H), 5.61 (d, J=4.8 Hz, 1H), 4.98 (d, J=
4.4 Hz, 1H); 13C NMR: d=162.4 (d, 1J=245.9 Hz), 151.8,
138.8, 136.6 (d, 4J=2.5 Hz), 129.0 (d, 3J=8.1 Hz), 126.2,
116.6 (d, 2J=21.5 Hz), 112.2, 61.1; ATR-FTIR: n=3390,
2923, 2360, 2344, 1597, 1507, 1472, 1320, 1309, 1224, 1158,
1113, 1097, 862, 852, 800, 788, 776 cmÀ1; MS (EI): m/z (%)=
340 (M), 203 (100), 183, 107, 76, 30; HR-MS (ESI): m/z=
341.1098, calcd. for C19H15F2N2O2 (M+H): 341.1096.
1
1:10, Rf =0.4). H NMR: d=9.16 (d, J=2.4 Hz, 1H), 9.08 (d,
J=4.8 Hz, 1H), 8.15 (dd, J=9.6, 2.4 Hz, 1H), 7.41–7.32 (m,
10H), 6.81 (d, J=9.2 Hz, 1H), 5.82 (d, J=5.6 Hz, 1H);
13C NMR: d=147.2, 139.8, 136.7, 131.2, 130.2, 129.4, 128.5,
127.1, 124.0, 115.3, 62.5; ATR-FTIR: n=3367, 3061, 2028,
2955, 2924, 2852, 1616, 1597, 1520, 1503, 1471, 1454, 1425,
N-(Di-p-tolylmethyl)-4-nitroaniline (3o): Isolated by flash
column chromatography (ethyl acetate/petroleum ether=
1
1:10, Rf =0.6). H NMR: d=8.01 (d, J=8.8 Hz, 2H), 7.20–
1307, 1281, 1182, 1111, 1089, 1069, 968, 833, 745, 698 cmÀ1
;
7.15 (m, 8H), 6.49 (d, J=9.2 Hz, 2H), 5.57 (d, J=4.8 Hz,
1H), 4.99 (d, J=4.8 Hz, 1H), 2.34 (s, 6H); 13C NMR: d=
152.2, 138.4, 138.3, 137.7, 129.7, 127.2, 126.2, 112.1, 61.9,
21.1; ATR-FTIR: n=3376, 2923, 1736, 1598, 1502, 1473,
MS (EI): m/z (%)=349 (M), 285, 272, 210, 183, 167 (100),
165, 127, 105, 85, 71, 57, 43; HR-MS (ESI): m/z=350.1130,
calcd. for C19H16N3O4 (M+H):350.1135.
Adv. Synth. Catal. 0000, 000, 0 – 0
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Wenjuan Li et al.
FULL PAPERS
1320, 1309, 1277, 1184, 1111, 1077, 1045, 833, 764, 753,
718 cmÀ1; MS (EI): m/z (%)=332 (M), 302, 195 (100), 180,
165, 152, 141, 107, 105, 84, 77, 65, 43, 30, 26; HR-MS (ESI):
m/z=333.1597, calcd. for C21H21N2O2 (M+H): 333.1598.
N-(Di-p-tolylmethyl)-4-methylaniline (3p): Isolated by
flash column chromatography (ethyl acetate/petroleum
(EI): m/z (%)=248 (M), 131 (100), 103, 91, 77, 58, 43, 28;
HR-MS (ESI): m/z=249.1385, calcd. for C17H17N2 (M+H):
249.1386.
N-(4-Nitrophenyl)-2,3-dihydro-1H-inden-1-amine
(3w):
Isolated by flash column chromatography (ethyl acetate/pe-
troleum ether=1:10, Rf =0.3). 1H NMR: d=8.12 (d, J=
9.2 Hz, 2H), 7.35–7.30 (m, 3H), 7.28–7.22 (m, 1H), 6.64 (d,
J=9.2 Hz, 2H), 5.10 (dt, J=6.8, 7.2 Hz, 1H), 4.73 (d, J=
7.2 Hz, 1H), 3.07 (ddd, J=13.6, 8.4, 4.8 Hz, 1H), 2.95 (dt,
J=15.6, 7.6 Hz, 1H), 2.68–2.60 (m, 1H), 2.01–1.92 (m, 1H);
13C NMR: d=152.7, 143.6, 142.7, 128.6, 127.0, 126.5, 125.2,
124.1, 111.4, 58.3, 33.5, 30.2. ATR-FTIR: n=3390, 2910,
2875, 1598, 1501, 1473, 1303, 1184, 1111, 833, 753 cmÀ1; MS
(EI): m/z (%)=254 (M), 117 (100), 115, 91, 65, 57; HR-MS
(ESI): m/z=255.1126, calcd. for C15H15N2O2 (M+H):
255.1128.
1
ether=1:30, Rf =0.6). H NMR: d=7.22 (d, J=8.0 Hz, 4H),
7.11 (d, J=8.0 Hz, 4H), 6.91 (d, J=8.4 Hz, 2H), 6.45 (d, J=
8.4 Hz, 2H), 5.39 (s, 1H), 4.07 (s, 1H), 2.31 (s, 6H), 2.20 (s,
3H); 13C NMR: d=145.3, 140.4, 136.8, 129.6, 129.3, 127.2,
113.5, 62.7, 21.1, 20.3; ATR-FTIR: n=3411, 3020, 2921,
2861, 2363, 1617, 1518, 1473, 1315, 1301, 1264, 1183, 1126,
1020, 846, 806, 781, 767 cmÀ1; MS (EI): m/z (%)=301 (M),
195 (100), 180, 165, 91, 58, 43, 28; HR-MS (ESI): m/z=
300.1739, calcd. for C22H22N (M+): 300.1747.
(E)-N-(1,3-Diphenylallyl)-4-nitroaniline (3q):[37] Isolated
by flash column chromatography (ethyl acetate/petroleum
N-(CyclopropylACHTUNTRGNEUNG(phenyl)methyl)-4-nitroaniline (3x): Isolat-
1
ether=1:10, Rf =0.5). H NMR: d=8.05 (d, J=8.8 Hz, 2H),
ed by flash column chromatography (ethyl acetate/petrole-
1
7.40–7.23 (m, 10H), 6.62–6.56 (m, 3H), 6.37 (dd, J=16.0,
6.4 Hz, 1H), 5.20 (t, J=4.8 Hz, 1H), 4.93 (d, J=4.0 Hz,
1H); 13C NMR: d=152.1, 140.3, 138.5, 136.0, 132.3, 129.2,
128.7, 128.6, 128.2, 128.1, 127.2, 126.6, 126.3, 112.1, 60.1.
4-Nitro-N-(1-phenylethyl)aniline (3r):[30] Isolated by flash
column chromatography (ethyl acetate/petroleum ether=
um ether=1:10, Rf =0.6). H NMR: d=7.97 (d, J=9.6 Hz,
2H), 7.37–7.28 (m, 5H), 6.41 (d, J=9.2 Hz, 2H), 5.19 (d, J=
4.0 Hz, 1H), 3.84 (dd, J=8.0, 4.4 Hz, 1H), 1.27–1.19 (m,
1H), 0.71–0.57 (m, 2H), 0.51–0.45 (m, 1H), 0.42–0.36 (m,
1H); 13C NMR: d=152.4, 141.1, 138.1, 128.8, 127.6, 126.3,
126.1, 111.9, 62.3, 19.0, 4.2, 3.4; ATR-FTIR: n=3362, 2922,
2852, 1597, 1516, 1501, 1468, 1311, 1300, 1273, 1182, 1111,
831, 752, 700 cmÀ1; MS (EI): m/z (%)=268 (M), 242,224,
147, 131 (100), 105, 91, 77, 57, 43, 29; HR-MS (ESI): m/z=
269.1283, calcd. for C16H17N2O2 (M+H): 269.1285.
4-Benzhydryl-2,3,5,6-tetrafluoroaniline (4): Isolated by
flash column chromatography (ethyl acetate/petroleum
ether=1:20, Rf =0.4). 1H NMR: d=7.31–7.18 (m, 10H),
5.80 (s, 1H), 3.90 (s, 2H); 13C NMR: d=145.1(dm,
JF=240.1 Hz), 141.1, 136.8(dm, JF=239.4 Hz), 128.7, 128.4,
126.7, 125.1(m), 109.4(t, JF=17.1 Hz), 45.5; ATR-FTIR: n=
3396, 2998, 2901, 2361, 1667, 1600, 1516, 1495, 1453, 1296,
1170, 1136, 1032, 978, 941, 912, 823, 738 cmÀ1; MS (EI): m/z
(%)=331 (M), 310, 254, 234, 213, 207, 165, 152, 85, 71, 57,
32; HR-MS (ESI): m/z=332.1054, calcd. for C19H14F4N
(M+H): 332.1057.
1
1:10, Rf =0.5). H NMR: d=7.99 (d, J=9.2 Hz, 2H), 7.36–
7.25 (m, 5H), 6.46 (d, J=9.2 Hz, 2H), 4.91 (s, 1H), 4.59
(hep, J=6.4 Hz, 1H), 1.57 (d, J=6.8 Hz, 3H); 13C NMR:
d=152.4, 143.3, 138.1, 129.0, 127.5, 126.3, 125.7, 111.9, 53.3,
24.5.
2,4-Dinitro-N-(1-phenylethyl)aniline (3s):[38] Isolated by
flash column chromatography (dichloromethane/petroleum
1
ether=1:1, Rf =0.2). H NMR: d=9.12 (d, J=2.8 Hz, 1H),
8.89 (d, J=4.8 Hz, 1H), 8.08 (dd, J=9.6, 2.4 Hz, 1H), 7.40–
7.29 (m, 5H), 6.74 (d, J=9.6 Hz, 1H), 4.79 (hep, J=6.8 Hz,
1H), 1.72 (d, J=6.8 Hz, 3H); 13C NMR: d=147.5, 141.9,
136.4, 130.7, 130.1, 129.4, 128.1, 125.5, 124.1, 115.3, 53.9,
24.7.
4-Methyl-N-(1-phenylethyl)benzenesulfonamide
(3t):[34]
Isolated by flash column chromatography (ethyl acetate/pe-
troleum ether=1:5, Rf =0.3). 1H NMR: d=7.62 (d, J=
8.4 Hz, 2H), 7.20–7.15 (m, 5H), 7.11–7.09 (m, 2H), 5.28 (s,
1H), 4.45 (hep, J=6.8 Hz, 1H), 2.37 (s, 3H), 1.40 (d, J=
6.8 Hz, 3H); 13C NMR: d=143.0, 142.1, 137.6, 129.4, 128.4,
127.3, 127.0, 126.1, 53.6, 23.5, 21.4.
4-Benzhydryl-2-nitroaniline (5): Isolated by flash column
chromatography (ethyl acetate/petroleum ether=1:10, Rf =
1
0.4). H NMR: d=7.85
N
(m, 5H), 6.73 (d, J=8.8 Hz, 1H), 6.01 (s, 1H), 5.44 (s, 1H);
13C NMR: d=143.3, 143.0, 136.9, 132.9, 131.8, 129.1, 128.5,
126.6, 125.9, 118.9, 55.5; ATR-FTIR: n=3375, 2962, 2922,
1583, 1562, 1514, 1469, 1410, 1339, 1261, 1091, 1020, 862,
800, 698 cmÀ1; MS (EI): m/z (%): 304 (M, 100), 287, 269,
257, 227, 192, 180, 152, 122, 115, 92, 77, 51; HR-MS (ESI):
m/z=305.1280, calcd. for C19H17N2O2 (M+H): 305.1285.
4-Benzhydryl-2,6-dichlorophenylamine (6): Isolated by
flash column chromatography (dichloromethane/petroleum
ether=1:10, Rf =0.5). 1H NMR: d=7.30–7.27 (m, 4H),
7.24–7.20 (m, 2H), 7.09–7.07 (m, 4H), 6.93 (s, 2H), 5.38 (s,
1H), 4.35 (s, 2H); 13C NMR: d=143.2, 138.4, 134.4, 129.2,
128.6, 128.4, 126.5, 119.5, 55.6; ATR-FTIR: n=3485, 3387,
3084, 3059, 3024, 2924, 2853, 1614, 1580, 1557, 1480, 1450,
1410, 1308, 1294, 1258, 1229, 1190, 1076, 1030, 887, 851, 816,
779, 758, 736, 700, 602 cmÀ1; MS (EI): m/z (%)=327 (M),
316, 294, 292, 256, 250, 223, 211, 197, 155, 127, 113, 105, 85,
N-(4-Nitrophenyl)-1,2,3,4-tetrahydronaphthalen-1-amine
(3u):[30] Isolated by flash column chromatography (ethyl ace-
1
tate/petroleum ether=1:10, Rf =0.4). H NMR: d=8.10 (d,
J=9.2 Hz, 2H), 7.30–7.28 (m, 1H), 7.25–7.14 (m, 3H), 6.60
(d, J=9.2 Hz, 2H), 4.77–4.71 (m, 2H), 2.91–2.75 (m, 2H),
2.08–1.95 (m, 2H), 1.93–1.80 (m, 2H); 13C NMR: d=152.3,
137.8, 137.7, 136.1, 129.4, 128.9, 127.8, 126.6, 126.4, 111.1,
51.0, 29.0, 28.7, 19.3.
4-(1,2,3,4-Tetrahydronaphthalen-1-ylamino)benzonitrile
(3v): Isolated by flash column chromatography (ethyl ace-
1
tate/petroleum ether=1:10, Rf =0.4). H NMR: d=7.44 (d,
J=8.8 Hz, 2H), 7.31–7.29 (m, 1H), 7.24–7.13 (m, 3H), 6.62
(d, J=8.8 Hz, 2H), 4.69–4.65 (m, 1H), 4.42 (d, J=8.0 Hz,
1H), 2.89–2.74 (m, 2H), 2.04–1.93 (m, 2H), 1.91–1.79 (m,
2H); 13C NMR: d=150.3, 137.6, 136.6, 133.8, 129.3, 128.9,
127.6, 126.3, 120.4, 112.2, 98.5, 50.7, 29.1, 28.6, 19.3; ATR-
FTIR: n=3675, 3365, 2924, 2360, 2212, 1604, 1519, 1490,
1454, 1377, 1337, 1259, 1174, 1066, 824, 774, 742 cmÀ1; MS
71, 57
ACHTUNGTREN(NGNU 100), 43, 29; HR-MS (ESI): m/z=328.0663, calcd. for
C19H16Cl2 (M+H):328.0654.
8
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ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
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À
À
Iron-Catalyzed C C Bond Cleavage and C N Bond Formation
1,2-Dihydronaphthalene (9):[39] Isolated by flash column
chromatography (ethyl acetate/petroleum ether=1:30, Rf =
0.8). 1H NMR: d=7.16–7.06 (m, 3H), 7.02–7.00 (m, 1H),
6.46 (dt, J=9.6, 1.6 Hz, 1H), 6.02 (dt, J=9.6, 4.4 Hz, 1H),
2.79 (t, J=8.4 Hz, 2H), 2.31 (tdd, J=8.4, 4.0, 1.6 Hz, 2H);
13C NMR: d=135.4, 134.1, 128.6, 127.8, 127.5, 126.8, 126.4,
125.8, 27.5, 23.2.
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(E)-4-Nitro-N-(4-phenylbut-3-enyl)aniline (10): Isolated
by flash column chromatography (ethyl acetate/petroleum
1
ether=1:10, Rf =0.5). H NMR: d=8.08 (d, J=9.2 Hz, 2H),
7.37–7.30 (m, 4H), 7.25–7.22 (m, 1H), 6.54–6.49 (m, 3H),
6.19 (dt, J=16.0, 6.8 Hz, 1H), 4.61 (s, 1H), 3.38–3.34 (m,
2H), 2.61–2.56 (m, 2H); 13C NMR: d=153.3, 138.0, 136.9,
133.0, 128.7, 127.6, 126.5, 126.2, 111.2, 42.7, 32.5; ATR-
FTIR: n=3370, 3024, 2924, 1599, 1526, 1501, 1470, 1321,
1304, 1280, 1184, 1111, 964, 831, 752, 692 cmÀ1; MS (EI):
m/z (%)=268 (M), 152, 151 (100), 117, 105, 84, 77, 57, 43;
HR-MS (ESI): m/z=269.1285, calcd. for C16H17N2O2 (M+
H): 269.1285.
N,N-Bis[(E)-4-phenylbut-3-en-1-yl]argonamine (11): Iso-
lated by flash column chromatography (ethyl acetate/petro-
1
leum ether=1:10, Rf =0.4). H NMR: d=8.14 (d, J=9.2 Hz,
2H), 7.34–7.28 (m, 8H), 7.25–7.21 (m, 2H), 6.66 (d, J=
9.6 Hz, 2H), 6.47 (d, J=16.0 Hz, 2H), 6.18 (dt, J=16.0,
7.2 Hz, 2H), 3.56 (t, J=7.2 Hz, 4H), 2.56 (q, J=7.2 Hz,
4H); 13C NMR: d=152.2, 136.9, 136.8, 132.7, 128.6, 127.5,
126.4, 126.0, 125.8, 110.3, 51.3, 30.8; ATR-FTIR: n=3024,
2953, 2922, 2851, 2683, 2421, 2357, 2337, 1733, 1591, 1514,
1485, 1404, 1303, 1290, 1197, 1113, 966, 824, 741, 692 cmÀ1
;
HR-MS (ESI): m/z=399.2066, calcd. for C26H27N2O2 (M+
H): 399.2067.
[10] A. Wilsily, Y. Nguyen, E. Fillion, J. Am. Chem. Soc.
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Financial support by the National Science Foundation of
China (20832002 and 21072223), the Fundamental Research
Funds for the Central Universities, and the Research Funds
of Renmin University of China (10XNL017).
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Iron-Catalyzed C C Bond Cleavage and C N Bond
Formation
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Adv. Synth. Catal. 2013, 355, 1 – 11
Wenjuan Li, Xiaojian Zheng, Zhiping Li*
Adv. Synth. Catal. 0000, 000, 0 – 0
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