Bi(iii)-catalyzed aminooxygenation of propargyl amidines to synthesize 2-fluoroalkyl imidazole-5-carbaldehydes and their decarbonylations

Article abstract of DOI:10.1039/d0cc02143a

The first example of main group metal Bi(iii)-catalyzed aminooxygenation of fluorinated propargyl amidines was developed to produce 2-fluoroalkyl imidazole-5-carbaldehydes in moderate to excellent yields, in which phenol played a critical role and could be recovered and recycled. In the presence of KOt-Bu, an unconventional decarbonylation occurred on the 2-fluoroalkyl imidazole-5-carbaldehydes.

Full text of DOI:10.1039/d0cc02143a

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Conformational control of nonplanar free base porphyrins:
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Authors
Shan Li,*a
Yajun Li,b
Bin Feng,a
Jian Liang,a
Geyun You,a
Xiaofeng Liu,a
and Liqing Xianc
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DOI: 10.1039/D0CC02143A
Affiliations
a Key Laboratory of Regional Ecological Environment Analysis and Pollution Control of West
Guangxi, College of Chemistry and Environment Engineering, Baise University. 21 Zhongshan No.2
Road, Baise, 533000, China. E-mail: lishan0914@163.com
b State Key Laboratory of Structural Chemistry, Key Laboratory of Coal to Ethylene Glycol and Its
Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the
Structure of Matter, University of Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou,
350002, China.
c School of Materials Science and Engineering, Baise University, Baise 533000, China.
Acknowledgements
These works were supported by the National Natural Science Foundation of Guangxi
(2017GXNSFBA198225) and the project of promoting the baseline capacity of young teachers in
Guangxi (2017KY0719).
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Bi(III)-Catalyzed Aminooxygenation of Propargyl Amidines to
Synthesize 2-Fluoroalkyl Imidazole-5-Carbaldehydes and Their
Decarbonylations
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
The first example of main group metal Bi(III)-catalyzed benzylic or allylic oxidations to carbonylated derivatives with t-
1
2
aminooxygenation of fluorinated propargyl amidines was BuOOH , bismuth-catalyzed oxidations of alcohols to
1
3
developed to produce 2-fluoroalkyl imidazole-5-carbaldehydes in aldehydes or ketones with HNO
3 x y z
or peroxide , and Bi M O (M
moderate to excellent yields, in which phenol played a critical role = Mo, W, V)-catalyzed oxidation of propylene to epoxypropane
1
4
and could be recovered and recycled. In the presence of KOt-Bu, or acrolein with dioxygen (Scheme 1-A). In these oxidation
an unconventional decarbonylation occurred on the 2-fluoroalkyl reactions, external strong oxidants were required, and bismuth
imidazole-5-carbaldehydes.
salts were used as Lewis acids to modify the reactivity of
external oxidants. Herein, we reported a novel bismuth-
catalyzed aminooxygenation of fluorinated propargyl amidines
to synthesize 2-fluoroalkyl imidazole-5-carbaldehydes (Scheme
1
Aminooxygenation of C-C multiple bonds is one of the most
straightforward approaches to synthesize vicinal amino alcohol
derivatives. In studies focusing on developing a simple and
efficient method, many transition-metal catalysts, including
1
-B). In this process, the terminal alkynyl carbon atom is
transformed to carbonyl group efficiently with concurrent
formation of 2-fluoroalkyl imidazole ring, which allows for
quickly accessing a large number of diverse 2-fluoroalkyl
imidazole derivatives for drug discovery. To the best of our
knowledge, this is the first example of main group metal-
catalyzed aminooxygenation. Unlike traditional bismuth-
catalyzed oxidation reactions, the external additive that is
needed to achieve satisfactory results can be recovered and
recycled.
2
3
4
5
6
palladium , gold , copper , iron , and toxic osmium salts , have
been explored. Although great successes have been achieved,
the necessities of harsh reaction conditions, precious metal
catalysts/ligands, or toxic organic reagents hinder the
application of these protocols. With the goal of providing more
sustainable strategies in catalysts, increasing efforts have been
made to unlock the potential of main group elements to
7
,8
emulate the catalytic reactivity of transition metals recently .
In this regard, the environmental friendliness of bismuth salts
whose toxicity is even less than table salt, and associated with
low cost, make them attractive and practical catalysts.
Scheme 1. Bismuth-catalyzed oxidation reactions
(A) Previous works: bismuth-catalyzed oxidation reactions
As the heaviest stable metal in the periodic table, bismuth
offers many unique properties ; for example, various bismuth
OH
9
Ar
R
Bi(III)
+
oxidant
salts have been demonstrated as Lewis acidic catalysts and
1
0
been widely applied in organic synthesis . Organobismuth
compounds, such as BiPh and BiPh Cl , can be used in
O
3
3
2
O
Ar
R
transition metal-catalyzed cross-coupling reactions to
construct carbon-carbon bond and Carbon-heteroatom
(
B) This work: bismuth(III)-catalyzed aminooxygenation
1
1
bond . Most notably, bismuth salts as main group metal
catalysts are potentially valuable in organic oxidation
reactions. Some works on this topic include bismuth-catalyzed
Ar
Ar
N
N
Bi(III) catalyst
Rf
O
H
Rf
N
H
phenol, O2
N
low toxicity and low catalyst loading
high functional group tolerance
phenol can be recovered and recycled
mild reaction conditions
moderate to excellent yield
high atomic economy
a.
Address here
Address here
Address here
b.
c.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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Table 1. Optimized for Bi-catalyzed aminooxygenationa
Journal Name
19). Additives were also examined to improve this
View Article Online
DOI: 10.1039/D0CC02143A
transformation. To our delight, 2a was obtained in an excellent
Ar
Ar
N
N
F3C
Bismuth salts
O
H
yield of 94% when 3.0 equiv of phenol was added (Table 1,
entry 23). Furthermore, the reaction gave 2a in an identical
yield when the loadings of catalyst and phenol were decreased
to 1.0 mol% and 1.5 equiv respectively, which were taken as
the optimal reaction conditions (Table 1, entry 26). With less
than 1.5 equiv of phenol, the conversion of 1a decreased, and
the yield of 2a dropped below 50% (Table 1, entry 27).
Interestingly, almost no consumption of phenol was observed
in the reaction as which could be quantitatively recovered.
Moreover, the recovered phenol could be reused and 2a was
obtained in a good yield of 71% (Table 1, entry 28). Control
F3C
N
H
additive
solvent, T, O2
N
1a
2a
Catalyst
T
Additive
Yield
(%)b
36
- c
Entry
solvent
(
equiv)
.5H
O (0.1)
(℃)
60
60
60
60
60
60
60
60
60
60
60
60
50
60
50
60
75
35
35
35
35
35
35
35
35
35
35
35
35
35
(equiv)
1
2
3
4
5
6
7
8
9
Bi(NO
3
)
3
2
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
3
CN
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
Bi(O)Cl (0.1)
Bi
BiPh
Bi(OTf)
BiI (0.1)
BiCl (0.1)
NaBiO .
2H O (0.1)
BiPh Cl (0.1)
BiPh (OAc) (0.1)
BiPh CO (0.1)
O
2 3
(0.1)
-
3
(0.1)
26
11d
40
45
-
3
(0.1)
3
experiments showed that no reaction occurred without BiCl
or under an Ar atmosphere (Table S1, entries 29-30).
3
3
3
2
-catalyzed aminooxygenationa
Table 2. Scope of BiCl
3
3
2
-
Ar
N
Ar
N
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
2
-
BiCl3 (1.0 mol %)
Rf
O
H
3
3
-
Rf
N
H
Phenol (1.5 equiv)
acetone, 35 oC, O2
N
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
BiCl
3
3
3
3
3
3
3
3
3
3
3
3
3
(0.1)
(0.1)
(0.1)
(0.1)
(0.1)
(0.1)
(0.1)
(0.1)
(0.1)
(0.1)
(0.1)
(0.1)
(0.1)
acetone
THF
47
41
34
12
-
1
2
DMF
CH3
OCH3
CN
NO2
COOEt
2 2
CH Cl
toluene
acetone
acetone
acetone
acetone
acetone
acetone
acetone
acetone
acetone
acetone
acetone
acetone
acetone
acetone
F3C
F3C
F3C
F3C
F3C
F3C
N
O
N
O
H
N
O
H
N
O
N
O
H
N
O
H
42
46
/e,f
47
56
49
94g
-
96h
94i
47j
71k
-l
N
N
N
N
N
N
H
H
2a, 95%
2b, 95%
2c, 97%
2d, 83%
2e, 67%
2f, 85%
2 3
K CO (1.0)
Cl
2
H O (3.0)
CH3
Cl
CF3
H3CO
F3C
CH
3
OH (3.0)
F3C
F3C
F3C
F3C
N
O
H
N
O
H
N
O
H
N
O
H
N
O
H
PhCOOH (3.0)
Phenol (3.0)
HCl (3.0)
N
N
N
N
N
2g, 93%
2h, 90%
2i, 76%
2j, 83%
2k, 94%
OCH3
CF3
BiCl
BiCl
BiCl
BiCl
3
3
3
3
(0.01)
(0.01)
(0.01)
(0.01)
-
Phenol (3.0)
Phenol (1.5)
Phenol (1.0)
Phenol (1.5)
Phenol (1.5)
Phenol (1.5)
Br
Ph
Et
F3C
F3C
2
ClF C
2
ClF C
2
ClF C
N
N
O
H
N
O
H
N
N
O
H
N
O
N
N
O
H
N
N
H
2l, 89%
2m, 92%
2n, 80%
2o, 64%
2p, 78%
CH3
CN
OCH3
BiCl
3
(0.01)
-m
Br
a
(balloon), 6 h. b
2
HF C
Reaction conditions: 1a (0.5 mmol), solvent (5.0 mL), O
2
ClF2C
N
O
H
BrF2C
N
O
H
BrF2C
N
O
H
N
O
H
HF2C
N
O
H
c
d
e
Isolated yield. “-” No reaction. Yield of 5-methyl imidazole. “/” No
N
N
N
N
N
f
g
desired product. A same result with Et
3
N (1.0 equiv). 92% of Phenol was
h
I
j
2q, 74%
2r, 66%
2s, 53%
OCH3
OCH3
2t, 92%
2u, 95%
recovered. 94% of Phenol was recovered. 93% of Phenol was recovered.
3% of Phenol was recovered. Recovered phenol was used, and 91% of
Phenol was recovered. No reaction without BiCl . No reaction under Ar.
3
k
8
OCH3
l
m
Our exploration of the optimal reaction conditions for this
new transformation was commenced with N-phenyl N’-
F3CF2C
F3CF2CF2C
F3C
N
EtOOC
N
O
H
N
O
H
N
O
O
N
H
H
H
N
N
N
N
H
H
propargyl 2-trifluoromethyl amidine 1a. Using 10 mol% of
2x, 27b
2v, 91%
2w, 83%
2y, 93%
2z, 71%
.
Bi(NO
)
3 3
2
5H O as the catalyst and CH
3
CN as the solvent, 1a was
converted to 2-trifluoromethyl imidazole-5-carbaldehyde 2a in
an acceptable yield of 36% at 60 ℃ under a dioxygen acetone (6.0 mL), 35 ℃, O
a
Reaction conditions: 1 (0.5 mmol), BiCl
3
(1.0 mol%), phenol (1.5 equiv),
, 6 h. b 57% of substrate was recovered.
2
atmosphere (Table 1, entry 1). Screening other bismuth salts
showed that some Bismuth(III) salts could impel the
proceeding of aminooxygenation, of which BiCl was the
3
suitable one for achieving this transformation with a higher
yield (Table 1, entries 2-7). While, no reaction occurred when
Bismuth(V) salts were used as catalysts (Table 1, entries 8-11).
Solvents, reaction temperature, and bases were all examined,
but the yield of 2a remained below 50% (Table 1, entries 12-
3
Then, the generality of BiCl -catalyzed aminooxygenation
was investigated under the optimal reaction conditions, and
the results are summarized in Table 2. The reaction showed
good functional group compatibility, as various substituted
substrates produced the corresponding products in moderate
to excellent yields. Perfluoroalkyl substrates bearing electron-
donating groups (Me and OMe) gave the desired products in
excellent yields (2b, 2c, 2h and 2k). Electron-withdrawing
2
| J. Name., 2012, 00, 1-3
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groups usually led to lower yields (2d, 2e, 2f and 2j). Compared Table 3. Scope of KOt-Bu-mediated decarbonylationa
View Article Online
DOI: 10.1039/D0CC02143A
with electronic effect, steric hindrance was found to have little
influence on the efficiency of this aminooxygenation (2c and
Ar
N
Ar
Rf
KOt-Bu (3.0 equiv)
Rf
O
H
N
DMF, 45 oC, Ar
H
N
2
k). However, low yields were often obtained for substrates
with a XCF - group, especially BrCF -, because of their
instability (2n-2s). The reactions of substrates with a HCF
N
2
2
2
3
2
-
CH3
Cl
COOEt
group proceeded without any difficulty and gave the desired
products in excellent yields (2t and 2u). Aminooxygenation of
nonfluorinated amidine was also efficient under the standard
reaction conditions and an excellent yield was obtained (2y).
Unfortunately, this method was not suitable for internal alkyne
substrate and amide. In these reactions, bismuth salt working
F3C
F3C
F3C
F3C
N
N
N
N
H
H
H
H
N
N
N
N
3d, 0b
3a, 84%
3b, 85%
3c, 69%
CN
CH3
Cl
1
5
just as Lewis acidic catalyst resulted in cyclized products (2x
and 2z).
F3C
F3C
F3C
OCH3
N
N
N
N
H
H
H
HO
N
N
In the course of investigating the properties of 2a, an
1
6
3e, 73%
3f, 73%
OCH3
3g, 43%
3h, 87%
unconventional decarbonylation process was observed in the
presence of strong base, whose efficiency would not be
damaged by the addition of TEMPO. And no deuterated
OCH3
product was detected when D
2
O was added to the model
F3C
Ph ClF2C
HF2C
F3CF2C
N
N
N
H
N
H
H
H
reaction (Scheme 2). In view of importance of this process,
further investigation was then carried out. Effects of various
parameters on this process were examined, and the results are
summarized in Table S1.
N
N
N
N
3
i, 69%
3j, 71%
3k, 76%
3l, 91%
a
Reactions conditions: substrate (1.0 mmol), KOt-Bu (3.0
equiv) in DMF (5.0 mL) at 45 ℃ under Ar atmosphere. b 4.0
equiv of KOt-Bu
Scheme 2. Control experiments of decarbonylation
N-(p-CN)phenyl 2-trifluoromethyl imidazole 3m is an
important intermediate for the synthesis of an imidazole
derivative that is a precursor of potent 5-lipoxygense inhibitor
Ph
N
Ph
N
F3C
KOt-Bu (3.0 equiv)
F3C
O
H
DMF, 45 oC, Ar
H
N
N
1
7
ZD2138 . The synthetic utility of these reactions described in
2
a
3a, 84%
NaOMe (3.0 equiv)
KOEt (3.0 equiv)
messy
messy
this paper was demonstrated by synthesizing 3m in three steps
on gram scale and easier operation (Scheme 3).
18
Ph
N
Ph
N
Scheme 3. A concise route for synthesizing imidazole
derivative of ZD2138
F3C
F3C
KOt-Bu (3.0 equiv)
F3C
O
H
H
TEMPO (1.0 equiv)
DMF, 45 oC, Ar
N
N
N
Cl
Cl
Cl
2
a
3a, 78%
BiCl3 (1.0 mol %)
KOt-Bu (3.0 equiv)
N
Ph
N
Ph
N
DMF, 45 oC, Ar
phenol (2.0 equiv)
acetone, 40 oC, O2
F3C
F3C
KOt-Bu (4.0 equiv)
N
O
H
N
O
H
F3C
F3C
N
H
H
N
N
H
D2O (1.0 equiv)
DMF, 45 oC, Ar
N
1g, 2 g
2g, 1.72 g (82%)
3c, 0.91 g (58%)
2a
3a, 74%
No deuteration
.
NiCl2 6H2O (5 mol %),
Zn(CN)2 (0.8 equiv)
CN
O
3
H CO
The optimal reaction conditions were identified as 3.0 equiv
of KOt-Bu in DMF at 45 ℃ under an argon atmosphere, which
was used to examine the scope of the KOt-Bu-mediated
decarbonylation of 2-fluoroalkyl imidazole-5-carbaldehydes
bearing various functional groups (Table 3). The electronic
properties of substituents on phenyl ring generally had a
significant effect on this process. Decarbonylation of
substrates with electron-donating groups (3b, 3f and 3h) and
weak electron-withdrawing groups (3c and 3g), as well as
sterically hindered ones (3h and 3j), proceeded smoothly to
give the desired products in moderate to good yields.
Substrate with -COOEt was incompatible with this process as
no reaction occurred even with 4.0 equiv of KOt-Bu (3d).
Unexpectedly, substrate with -CN resulted in the removal of
imidazolyl group and the formation of 4-hydroxyl benzonitrile
dppf (6 mol %), Zn (20 mol %)
DMAP (1.0 equiv)
ref. 17
O
CH3CN, 60 o
N2
C
F3C
N
H
F3C
N
N
H
N
3m, 0.54 g (62%)
In summary, we have achieved a simple, efficient, economic
and environmentally friendly BiCl -catalyzed
3
aminooxygenation. Under the standard reaction conditions,
propargyl amidines, including fluorinated and nonfluorinated
ones, were converted into imidazole-5-carbaldehydes which
can be served as intermediates in synthesizing bioactive
compounds with a 2-fluoroalkyl imidazole motif in moderate
to excellent yields. Phenol was crucial for obtaining the desired
products in satisfactory yields and could be recovered and
recycled. Based on preliminary mechanistic studies, the role of
phenol was considered to facilitate the turnover of bismuth
catalyst, which still needs to be well substantiated. By
treatment with KOt-Bu, an unconventional decarbonylations
(3e). Furthermore, this process was also applicable to
substrates with other fluoroalkyl groups, and good yields were
obtained (3j-3l).
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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COMMUNICATION
occurred on 2-fluoroalkyl
Electronic properties of substituents on phenyl ring played a
vital role on reaction mode. Further studies on the detailed
reaction pathway of BiCl -catalyzed aminooxygenation and
3
KOt-Bu-mediated decarbonylation and their utility in organic
synthesis are still underway in our laboratory.
Journal Name
9
1
(a) H. Suzuki and Y. Matano, OrganobismutVhiewcAhrteicmle iOsntlrinye,
imidazole-5-carbaldehydes.
Elsevier Science, Amsterdam, New York, 2001; (b) T. Ollevier,
DOI: 10.1039/D0CC02143A
Bismuth-Mediated Organic Reactions, Springer-Verlag,
Berlin, Heidelberg, 2012; (c) J. A. R. Salvador, S. A. C.
Figueiredo, R. M. A. Pinto and S. M. Silvestre, Future Med.
Chem. 2012, 4, 1495.
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Bothwell, S. W. Krabbe and R. S. Mohan, Chem. Soc. Rev.
Conflicts of interest
The authors declare no competing financial interest.
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9 A possible mechanism of BiCl -catalyzed aminooxygenation
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was proposed and shown in Scheme S4.
0 A possible mechanism of KOt-Bu-mediated decarbonylation
was proposed and shown in Scheme S6.
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4
| J. Name., 2012, 00, 1-3
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DOI: 10.1039/D0CC02143A
R
R
R
BiCl3
KOt-Bu
N
Rf
N
O
H
Rf
phenol
acetone, O2
N
DMF, Ar
H
Rf
N
N
N
H
low catalyst loading
up to 97% yield
mild conditions
12 examples
phenol can be recycled
high atomic economy
up to 91% yield
The first example of Bi(III)-catalyzed aminooxygenation was developed to synthesize
-fluoroalkyl imidazole-5-carbaldehydes that would decarbonylate efficiently in the
presence of KOt-Bu.
2