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Rapid synthesis of acyl fluorides from carboxylic acids with Cu(O2CCF2SO2F)2
Journal Pre-proofs Rapid Synthesis of Acyl Fluorides from Carboxylic Acids with Cu(O2CCF2SO2F)2 Bingjun Le, Hao Wu, Xiaojun Hu, Xiumiao Zhou, Yong Guo, Qing-Yun Chen, Chao Liu PII: DOI: Reference:
S0040-4039(20)31129-1 https://doi.org/10.1016/j.tetlet.2020.152624 TETL 152624
To appear in:
Tetrahedron Letters
Received Date: Revised Date: Accepted Date:
1 October 2020 26 October 2020 31 October 2020
Please cite this article as: Le, B., Wu, H., Hu, X., Zhou, X., Guo, Y., Chen, Q-Y., Liu, C., Rapid Synthesis of Acyl Fluorides from Carboxylic Acids with Cu(O2CCF2SO2F)2, Tetrahedron Letters (2020), doi: https://doi.org/ 10.1016/j.tetlet.2020.152624
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Communication
Rapid Synthesis Cu(O2CCF2SO2F)2
of
Acyl
Fluorides
from
Carboxylic
Acids
with
Bingjun Le,a ,# Hao Wu,b,# Xiaojun Hu,*a Xiumiao Zhou,c Yong Guo,b Qing-Yun Chen,b Chao Liu*a,b
School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418, China
a
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China b
School of Chemical Engineering and Food Science, Zhengzhou Institute of Technology, 18 Yingcai Street, Zhengzhou, 450044, China
c
*E-mail: [email protected]; [email protected] # These authors contributed equally.
ARTICLE INFO
ABSTRACT
Article history:
Acyl fluorides have moderate electrophilicity and a very good balance between stability and reactivity. Utilization of acyl fluorides as versatile building blocks in transition-metal catalysis attracts fast-growing and great attention recently. Development of rapid and operationally simple synthetic methods for acyl fluorides has always been desirable. We report herein a rapid, simple and efficient acyl fluoride synthesis from carboxylic acids with Cu(O2CCF2SO2F)2 as a deoxofluorination reagent. Notably, Cu(O2CCF2SO2F)2 was readily prepared in large scale from inexpensive starting material, and previously used as a good trifluoromethylating reagent.
Received Received in revised form Accepted Available online Keywords： Acyl fluoride Carboxylic acid Copper salt Deoxofluorination Synthetic methods
Introduction
Since acyl fluorides have moderate electrophilicity and a very good balance between stability and reactivity derived from the unique properties of the C-F bond, they are valuable alternatives to carboxylic acids or acyl chlorides in many synthetic transformations, which are typically utilized as efficient acylation reagents for various nucleophilic molecules with relatively lower reactivity [1,2] and for peptide synthesis [3-5]. Moreover, oxidative addition of acyl C-F bond to transition-metal complexes occurs easily under mild reaction conditions to generate the corresponding metal fluoride species, RCO[M]F and
R[M]F. They may enable base-free cross-couplings under appropriate conditions via activating the coupling partner by nucleophilic fluorine. Consequently, the utilization of acyl fluorides as versatile building blocks in transition-metal catalysis attracts fast-growing attention recently, which significantly enriches their chemistry and application [6,7]. In these transformations, acyl fluorides (RCOF) can serve as RCO source via acyl coupling [8-17], R source via decarbonylative coupling [18-23] or fluoride source in various fluorination reactions [24-29] depending on the reaction conditions used. Given their importance and valuable application, a number of elegant preparation methods for acyl fluorides have been developed in recent years, including fluorination of aldehydic C-H bonds
[30,31] and fluorocarbonylation of organic halides [32-36]. While Cl-F exchange of acyl chlorides can efficiently afford the corresponding acyl fluorides [37-42], the main and reliable routes for the synthesis of acyl fluorides remains the direct treatment of carboxylic acids with various deoxofluorination reagents [7]. Representative deoxofluorination reagents for acyl fluoride synthesis from carboxylic acids include α-fluoroamine reagents (Ishikawa’s and Yarovenko’s reagent, TFFH) [43-46], DAST [47,48], Deoxo-Fluor [49-51], XtalFluor-E [52], Fluolead [53,54], (Me4N)SCF3 [55], cyanuric fluoride [56], Ph3P/Cl3CCN/TBAF(t-BuOH)4 [57], PPh3/NBS/Et3N.3HF [58], PPh3/Selectflour [59], SO2F2/TBAX [60], benzene-1,3-disulfonyl fluoride/DIPEA/DBU [61], etc. Despite these notable advances, development of new, rapid and operationally simple methods for direct acyl fluoride synthesis from carboxylic acid has always been popular and desired. We have always been putting effort on developing new fluoroalkylating methods by using tetrafluoroethene-β-sultonebased fluorinating derivatives as reagents [62-69], which is easily synthesized from cheap industrial raw materials CF2=CF2 and SO3 in nearly quantitative yield [70,71]. Among them, methyl fluorosulfonyldifluoroacetate (FSO2CF2COOMe), developed for the first catalytic trifluoromethylation reaction of haloarenes, is a practical, inexpensive and efficient reagent for trifluoromethylation [64-67]. Recently, a new trifluoromethylating reagent Cu(O2CCF2SO2F)2 has been conveniently prepared from inexpensive starting materials on scale, and utilized to efficiently trifluoromethylate a variety of haloarenes in good-to-excellent yields with high functional group compatibility under mild conditions (Scheme 1a) [68]. During our ongoing effort in the application of this new reagent, a facile and effective synthesis of valuable acyl fluorides from abundant carboxylic acids was achieved by simple treatment of various carboxylic acids with Cu(O2CCF2SO2F)2 in MeCN at room temperature for 15 min, efficiently leading to the corresponding acyl fluorides in good yields (Scheme 1b). Herein, we present the results. (a) ArX (X = Br or I) Cu, DMF, rt, 12 h Previous work
Ar-CF3
O
OH
O MeO
Cu(O2CCF2SO2F)2
CF2H
(1.0 equiv) Na2CO3 (1.0 equiv)
O MeO
MeCN, rt, 1 h
OMe
F 2a 58% 19F NMR yield
1a
Scheme 2 Accidental discovery of acyl fluoride synthesis from carboxylic acids with Cu(O2CCF2SO2F)2.
Subsequent reaction condition optimization was carried out using p-methoxybenzoic acid 1a as the model substrate, Cu(O2CCF2SO2F)2 as a safe and convenient deoxofluorination reagent. As shown in Table 1, to our delight, extensive screening of reaction conditions demonstrated that simple treatment of 1a with 2.0 equiv of Cu(O2CCF2SO2F)2 in dry MeCN under Ar atmosphere at room temperature for 15 min provided optimal reaction conditions to generate the desired acyl fluoride 2a in a good yield of 84% (entry 1). Whereas utilization of DMF as the solvent produced 60% yield of 2a, replacement of MeCN with THF or DCM resulted in no observation of the desired product (entris 2 and 3). Notably, water was found to be harmful for the desired reaction since no formation of 2a was observed with the use of small amounts of water as the co-solvent (entry 4). Reaction temperatures had an obvious effect on the reaction, both 0 oC and 60 oC led to lower yields of the target product (entry 5 and 6). Moreover, the desired reactions proceeded fast and extended reaction time was not helpful to the reactions (entry 7 and 8). It should be mentioned that the increased equivalent of Cu(O2CCF2SO2F)2 did not have a significant effect on the reaction, while use of 1.0 equivalent of Cu(O2CCF2SO2F)2 resulted in lower yield of 2a (entry 9 and 10). Finally, an attempt at improving the reactions by utilizing some additives, such as NaHCO3, K2CO3, NEt3 or pyridine etc. met with failure (entries 11-14).
Table 1 Optimization of reaction conditions for acyl fluoride synthesis from carboxylic acids with Cu(O2CCF2SO2F)2a
Cu(O2CCF2SO2F)2 O
This work (b) RCOOH MeCN, rt, 15 min
R
F
O MeO
O
MeO
F
OH 1a 1.0 equiv
Scheme 1 Synthetic application of Cu(O2CCF2SO2F)2.
MeCN, rt, 15 min Cu(O2CCF2SO2F)2
2a
2.0 equiv
Entry
Variation from conditions
the
standard
Yield of 2a (%)b
Results and Discussion
1
none
84
Initially, during a research program, we tried to difluoromethylate p-methoxybenzoic acid (1a) with Cu(O2CCF2SO2F)2 according to our previous report that FSO2CF2COOH was used as a good difluoromethylating reagent for the difluoromethylation of various carboxylic acids [72,73]. To our surprise, no formation of the desired difluoromethylated product was observed, but the corresponding acyl fluoride 2a was formed in a good yield (Scheme 2). We then realized that Cu(O2CCF2SO2F)2 may be a good deoxofluorination reagent for acyl fluoride synthesis from inexpensive carboxylic acids.
2
DMF instead of MeCN
60
3
THF or DCM instead of MeCN
0
4
0.2 mL of H2O as a co-solvent
39
5
0 oC
47
6
60 oC
77
7
1h
82
8
12 h
84
9
1.0 equiv of Cu(O2CCF2SO2F)2
56
10
3.0 equiv of Cu(O2CCF2SO2F)2
87
11
1.0 equiv of NaHCO3 as an additive
80
1.0 equiv of K2CO3 as an additive
OH
O
Cu(O2CCF2SO2F)2
F
R 2
1 Aromatic carboxylic acids O
12
MeCN, rt, 15 min
O R
O
F
F
O
F
O F
OCH3 2a 57% (84%) 75% (5 mmol scale)
78
13
1.0 equiv of NEt3 as an additive
78
14
1.0 equiv of pyridine as an additive
80
O
2b 78%
F
2e 77%
2f (74%)
2g 74%
O
O
O
F
F
O
F
2l 24% O
O
Cl
O
N N
S
2m 40%
F
F
F
F
F
O S O
2k 38%
2j 40%
O
N
I 2h 49%
NO2
CN
Br
F
I
F
2i 52% (75%)
Table 2 Substrate scope for acyl fluoride synthesis from carboxylic acids with Cu(O2CCF2SO2F)2a
2d (76%) O
F
O
General reaction conditions: p-methoxybenzoic acid (1a, 0.2 mmol, 1.0 equiv), Cu(O2CCF2SO2F)2 (0.4 mmol, 2.0 equiv), in MeCN (2 mL) under Ar atmosphere at room temperature for 15 min. b Yields were determined by 19F NMR spectroscopy using trifluorotoluene as an internal standard.
O
O
O F
a
With the optimal reaction conditions established (Table 1, entry 1), the scope of carboxylic acids was carefully explored and the results were summarized in Table 2. A wide range of aromatic carboxylic acids with electron-donating, neutral, and electron-withdrawing substituents were rapidly converted into the corresponding acyl fluoride products in good yields after flash column chromatography on a pad of silica gel. However, substrates with electron-withdrawing substituents provide lower yields of the desired products (2j-2l). Halo-substituted benzoic acids generate the corresponding products in acceptable yields (2f-2i). Notably, heteroaromatic carboxylic acids are also applicable to the current transformation, though lower yields of the corresponding acyl fluoride products were formed (2m-2o). Unfortunately, amino-substituted benzoic acid can not be applied to the protocol and no desired product 2p was observed. Next, we examined the generality of a number of aliphatic and cinnamic carboxylic acids. All examined substrates including primary (2q2x), secondary (2y, 2z), and tertiary (2aa-2cc) aliphatic carboxylic acids were effectively transformed to the desired products. However, use of aliphatic carboxylic acid 1s as the substrate delivers lower yield of the desired product, probably due to solubility issues. Attempt to improve the reaction by utilization of other solvents including CH2Cl2, THF and DMF met with failure. The present protocol is also suitable for various cinnamic carboxylic acids and successfully leads to the corresponding cinnamoyl fluorides in acceptable yields (2dd2jj). Interestingly, there is no HF addition by-products with double bond formed. It is worth to point out that NMR yields are reported for some acyl fluorides with high volatility (2d, 2f, 2n, 2u) or unstablility upon purification (2o, 2v, 2z). Furthermore, another attractive feature of this protocol is illustrated by readily scale-up synthesis of 2a, a good anhydrous fluorine source for effective SNAr fluorination [27], on 5 mmol scale with a good isolated yield of the target product, thus demonstrating good scalability of the transformation.
2c 59%
H 2N
2o (38%)
2n (59%)
2p (0%)
Aliphatic or cinnamic carboxylic acids O O F
6
O
O F
10
2q 77% (93%)
F F
14 2s 35%
2r 80%
F
O
O
O O
O F
H
Cl
O 2v (86%)
2u (65%)
O F
O
O
O
F F
2z (69%)
F
O
O MeO
2dd 42%
2cc 52% (70%)
F
2ee 63%
O
O
Cl 2bb 55%
2aa 53%
F
O 2N
2x 75%
O
F
2y 20% (56%) O
F
O
H O
2w 74%
O O
O
H
F
2t 74%
O
F
Cl
F
2ff 47% O
F
O Ph
O
O
F
Cl 2gg 29%
2hh 66%
O
F 2ii 44%
2jj 45%
Standard reaction conditions: carboxylic acid (1, 0.4 mmol), Cu(O2CCF2SO2F)2 (0.8 mmol) in MeCN (4 mL) under Ar atmosphere at room temperature for 15 min. Yields of isolated products are given. Yields in parentheses were determined by 19F NMR spectroscopy using trifluorotoluene as an internal standard. a
To illustrate the synthetic application of acyl fluorides synthesized, further transformation of the acyl fluoride products was preliminarily investigated. As revealed in Scheme 3, the reactions of acyl fluoride 2a with either PhCH2NH2, pbromophenol, or PhCH2SH efficiently produced the corresponding amide 3 and esters 4 and 5 in excellent yields.
Additionally, the palladium/copper-catalyzed direct acylation of azoles with acyl fluoride 2a was carried out for the facile generation of ketone 6. All these examples demonstrate the diverse reactivity and application of valuable acyl fluorides.
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments O
PhCH2NH2 DIPEA, MeCN, rt
N H MeO
(A)
(B)
3 96%
O MeO Br
O
2a (C)
O MeO
F
p-bromophenol NEt3, DMF, rt
The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (Nos. 21421002, 21871283, 21737004, 21672239).
O
PhCH2SH NEt3, DMF, rt
S
MeO 5-phenyloxazole Pd(PPh3)4 (cat.), CuCl/PPh3 (cat.) K2CO3, toluene, 80 oC
4 91% N
O
Appendix A. Supplementary data
O
(D) 6 56%
5 99%
OMe
Scheme 3 Synthetic appliction of acyl flouride 2a
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With respect with the reaction mechanism, we suggest the following mechanistic pathway shown in Scheme 4. Carboxylic acids react with Cu(O2CCF2SO2F)2 to afford the reaction intermediate [A] and fluoride ion. The subsequent nucleophilic attack of fluoride ion at the carbonyl group of intermediate [A] finishes the desired acyl fluoride products. Notably, coordination of copper cation in the reaction system with carbonyl group of intermediate [A] may play an important role in the subsequent nucleophilic reaction since replacement of Cu(O2CCF2SO2F)2 with FSO2CF2COOMe results in no formation of the desired acyl product. It should be mentioned that the formation of difluorocarbene and CF3 ion via the decomposition of Cu(O2CCF2SO2F)2 occurs during the reactions, which might result in the use of more amounts of Cu(O2CCF2SO2F)2 as a
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OSO2CF2COO F
R
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Scheme 4 Proposed mechanistic pathway for acyl fluoride synthesis from carboxylic acids with Cu(O2CCF2SO2F)2
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Declaration of interests
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China b
School of Chemical Engineering and Food Science, Zhengzhou Institute of Technology, 18 Yingcai Street, Zhengzhou, 450044, China c
*E-mail: [email protected]; [email protected] # These authors contributed equally.
☒ The authors declare that they have no known
competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:
Cu(O2CCF2SO2F)2
O R
OH
MeCN, rt, 15 min
O R
F
35 examples
A simple, rapid and efficient acyl fluoride synthesis from inexpensive carboxylic acids with Cu(O2CCF2SO2F)2 as a deoxofluorination reagent, previously used as a good trifluoromethylating reagent, has been developed.
[75]
Highlights
Rapid synthesis of acryl fluorides from
[74]
carboxylic acids
Graphical Abstract
reagent instead of
Rapid Synthesis of Acyl Fluorides from Carboxylic Acids with Cu(O2CCF2SO2F)2 Bingjun Le,a ,# Hao Wu,b,# Xiaojun Hu,*a Xiumiao Zhou,c Yong Guo,b Qing-Yun Chen,b Chao Liu*a,b
Cu(O2CCF2SO2F)2 as
a
deoxofluorination
a trifluoromethylating
reagent
Capable of versatile derivatization and latestage functionalization
[76]
S0040-4039(20)31129-1 https://doi.org/10.1016/j.tetlet.2020.152624 TETL 152624
To appear in:
Tetrahedron Letters
Received Date: Revised Date: Accepted Date:
1 October 2020 26 October 2020 31 October 2020
Please cite this article as: Le, B., Wu, H., Hu, X., Zhou, X., Guo, Y., Chen, Q-Y., Liu, C., Rapid Synthesis of Acyl Fluorides from Carboxylic Acids with Cu(O2CCF2SO2F)2, Tetrahedron Letters (2020), doi: https://doi.org/ 10.1016/j.tetlet.2020.152624
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Communication
Rapid Synthesis Cu(O2CCF2SO2F)2
of
Acyl
Fluorides
from
Carboxylic
Acids
with
Bingjun Le,a ,# Hao Wu,b,# Xiaojun Hu,*a Xiumiao Zhou,c Yong Guo,b Qing-Yun Chen,b Chao Liu*a,b
School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418, China
a
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China b
School of Chemical Engineering and Food Science, Zhengzhou Institute of Technology, 18 Yingcai Street, Zhengzhou, 450044, China
c
*E-mail: [email protected]; [email protected] # These authors contributed equally.
ARTICLE INFO
ABSTRACT
Article history:
Acyl fluorides have moderate electrophilicity and a very good balance between stability and reactivity. Utilization of acyl fluorides as versatile building blocks in transition-metal catalysis attracts fast-growing and great attention recently. Development of rapid and operationally simple synthetic methods for acyl fluorides has always been desirable. We report herein a rapid, simple and efficient acyl fluoride synthesis from carboxylic acids with Cu(O2CCF2SO2F)2 as a deoxofluorination reagent. Notably, Cu(O2CCF2SO2F)2 was readily prepared in large scale from inexpensive starting material, and previously used as a good trifluoromethylating reagent.
Received Received in revised form Accepted Available online Keywords： Acyl fluoride Carboxylic acid Copper salt Deoxofluorination Synthetic methods
Introduction
Since acyl fluorides have moderate electrophilicity and a very good balance between stability and reactivity derived from the unique properties of the C-F bond, they are valuable alternatives to carboxylic acids or acyl chlorides in many synthetic transformations, which are typically utilized as efficient acylation reagents for various nucleophilic molecules with relatively lower reactivity [1,2] and for peptide synthesis [3-5]. Moreover, oxidative addition of acyl C-F bond to transition-metal complexes occurs easily under mild reaction conditions to generate the corresponding metal fluoride species, RCO[M]F and
R[M]F. They may enable base-free cross-couplings under appropriate conditions via activating the coupling partner by nucleophilic fluorine. Consequently, the utilization of acyl fluorides as versatile building blocks in transition-metal catalysis attracts fast-growing attention recently, which significantly enriches their chemistry and application [6,7]. In these transformations, acyl fluorides (RCOF) can serve as RCO source via acyl coupling [8-17], R source via decarbonylative coupling [18-23] or fluoride source in various fluorination reactions [24-29] depending on the reaction conditions used. Given their importance and valuable application, a number of elegant preparation methods for acyl fluorides have been developed in recent years, including fluorination of aldehydic C-H bonds
[30,31] and fluorocarbonylation of organic halides [32-36]. While Cl-F exchange of acyl chlorides can efficiently afford the corresponding acyl fluorides [37-42], the main and reliable routes for the synthesis of acyl fluorides remains the direct treatment of carboxylic acids with various deoxofluorination reagents [7]. Representative deoxofluorination reagents for acyl fluoride synthesis from carboxylic acids include α-fluoroamine reagents (Ishikawa’s and Yarovenko’s reagent, TFFH) [43-46], DAST [47,48], Deoxo-Fluor [49-51], XtalFluor-E [52], Fluolead [53,54], (Me4N)SCF3 [55], cyanuric fluoride [56], Ph3P/Cl3CCN/TBAF(t-BuOH)4 [57], PPh3/NBS/Et3N.3HF [58], PPh3/Selectflour [59], SO2F2/TBAX [60], benzene-1,3-disulfonyl fluoride/DIPEA/DBU [61], etc. Despite these notable advances, development of new, rapid and operationally simple methods for direct acyl fluoride synthesis from carboxylic acid has always been popular and desired. We have always been putting effort on developing new fluoroalkylating methods by using tetrafluoroethene-β-sultonebased fluorinating derivatives as reagents [62-69], which is easily synthesized from cheap industrial raw materials CF2=CF2 and SO3 in nearly quantitative yield [70,71]. Among them, methyl fluorosulfonyldifluoroacetate (FSO2CF2COOMe), developed for the first catalytic trifluoromethylation reaction of haloarenes, is a practical, inexpensive and efficient reagent for trifluoromethylation [64-67]. Recently, a new trifluoromethylating reagent Cu(O2CCF2SO2F)2 has been conveniently prepared from inexpensive starting materials on scale, and utilized to efficiently trifluoromethylate a variety of haloarenes in good-to-excellent yields with high functional group compatibility under mild conditions (Scheme 1a) [68]. During our ongoing effort in the application of this new reagent, a facile and effective synthesis of valuable acyl fluorides from abundant carboxylic acids was achieved by simple treatment of various carboxylic acids with Cu(O2CCF2SO2F)2 in MeCN at room temperature for 15 min, efficiently leading to the corresponding acyl fluorides in good yields (Scheme 1b). Herein, we present the results. (a) ArX (X = Br or I) Cu, DMF, rt, 12 h Previous work
Ar-CF3
O
OH
O MeO
Cu(O2CCF2SO2F)2
CF2H
(1.0 equiv) Na2CO3 (1.0 equiv)
O MeO
MeCN, rt, 1 h
OMe
F 2a 58% 19F NMR yield
1a
Scheme 2 Accidental discovery of acyl fluoride synthesis from carboxylic acids with Cu(O2CCF2SO2F)2.
Subsequent reaction condition optimization was carried out using p-methoxybenzoic acid 1a as the model substrate, Cu(O2CCF2SO2F)2 as a safe and convenient deoxofluorination reagent. As shown in Table 1, to our delight, extensive screening of reaction conditions demonstrated that simple treatment of 1a with 2.0 equiv of Cu(O2CCF2SO2F)2 in dry MeCN under Ar atmosphere at room temperature for 15 min provided optimal reaction conditions to generate the desired acyl fluoride 2a in a good yield of 84% (entry 1). Whereas utilization of DMF as the solvent produced 60% yield of 2a, replacement of MeCN with THF or DCM resulted in no observation of the desired product (entris 2 and 3). Notably, water was found to be harmful for the desired reaction since no formation of 2a was observed with the use of small amounts of water as the co-solvent (entry 4). Reaction temperatures had an obvious effect on the reaction, both 0 oC and 60 oC led to lower yields of the target product (entry 5 and 6). Moreover, the desired reactions proceeded fast and extended reaction time was not helpful to the reactions (entry 7 and 8). It should be mentioned that the increased equivalent of Cu(O2CCF2SO2F)2 did not have a significant effect on the reaction, while use of 1.0 equivalent of Cu(O2CCF2SO2F)2 resulted in lower yield of 2a (entry 9 and 10). Finally, an attempt at improving the reactions by utilizing some additives, such as NaHCO3, K2CO3, NEt3 or pyridine etc. met with failure (entries 11-14).
Table 1 Optimization of reaction conditions for acyl fluoride synthesis from carboxylic acids with Cu(O2CCF2SO2F)2a
Cu(O2CCF2SO2F)2 O
This work (b) RCOOH MeCN, rt, 15 min
R
F
O MeO
O
MeO
F
OH 1a 1.0 equiv
Scheme 1 Synthetic application of Cu(O2CCF2SO2F)2.
MeCN, rt, 15 min Cu(O2CCF2SO2F)2
2a
2.0 equiv
Entry
Variation from conditions
the
standard
Yield of 2a (%)b
Results and Discussion
1
none
84
Initially, during a research program, we tried to difluoromethylate p-methoxybenzoic acid (1a) with Cu(O2CCF2SO2F)2 according to our previous report that FSO2CF2COOH was used as a good difluoromethylating reagent for the difluoromethylation of various carboxylic acids [72,73]. To our surprise, no formation of the desired difluoromethylated product was observed, but the corresponding acyl fluoride 2a was formed in a good yield (Scheme 2). We then realized that Cu(O2CCF2SO2F)2 may be a good deoxofluorination reagent for acyl fluoride synthesis from inexpensive carboxylic acids.
2
DMF instead of MeCN
60
3
THF or DCM instead of MeCN
0
4
0.2 mL of H2O as a co-solvent
39
5
0 oC
47
6
60 oC
77
7
1h
82
8
12 h
84
9
1.0 equiv of Cu(O2CCF2SO2F)2
56
10
3.0 equiv of Cu(O2CCF2SO2F)2
87
11
1.0 equiv of NaHCO3 as an additive
80
1.0 equiv of K2CO3 as an additive
OH
O
Cu(O2CCF2SO2F)2
F
R 2
1 Aromatic carboxylic acids O
12
MeCN, rt, 15 min
O R
O
F
F
O
F
O F
OCH3 2a 57% (84%) 75% (5 mmol scale)
78
13
1.0 equiv of NEt3 as an additive
78
14
1.0 equiv of pyridine as an additive
80
O
2b 78%
F
2e 77%
2f (74%)
2g 74%
O
O
O
F
F
O
F
2l 24% O
O
Cl
O
N N
S
2m 40%
F
F
F
F
F
O S O
2k 38%
2j 40%
O
N
I 2h 49%
NO2
CN
Br
F
I
F
2i 52% (75%)
Table 2 Substrate scope for acyl fluoride synthesis from carboxylic acids with Cu(O2CCF2SO2F)2a
2d (76%) O
F
O
General reaction conditions: p-methoxybenzoic acid (1a, 0.2 mmol, 1.0 equiv), Cu(O2CCF2SO2F)2 (0.4 mmol, 2.0 equiv), in MeCN (2 mL) under Ar atmosphere at room temperature for 15 min. b Yields were determined by 19F NMR spectroscopy using trifluorotoluene as an internal standard.
O
O
O F
a
With the optimal reaction conditions established (Table 1, entry 1), the scope of carboxylic acids was carefully explored and the results were summarized in Table 2. A wide range of aromatic carboxylic acids with electron-donating, neutral, and electron-withdrawing substituents were rapidly converted into the corresponding acyl fluoride products in good yields after flash column chromatography on a pad of silica gel. However, substrates with electron-withdrawing substituents provide lower yields of the desired products (2j-2l). Halo-substituted benzoic acids generate the corresponding products in acceptable yields (2f-2i). Notably, heteroaromatic carboxylic acids are also applicable to the current transformation, though lower yields of the corresponding acyl fluoride products were formed (2m-2o). Unfortunately, amino-substituted benzoic acid can not be applied to the protocol and no desired product 2p was observed. Next, we examined the generality of a number of aliphatic and cinnamic carboxylic acids. All examined substrates including primary (2q2x), secondary (2y, 2z), and tertiary (2aa-2cc) aliphatic carboxylic acids were effectively transformed to the desired products. However, use of aliphatic carboxylic acid 1s as the substrate delivers lower yield of the desired product, probably due to solubility issues. Attempt to improve the reaction by utilization of other solvents including CH2Cl2, THF and DMF met with failure. The present protocol is also suitable for various cinnamic carboxylic acids and successfully leads to the corresponding cinnamoyl fluorides in acceptable yields (2dd2jj). Interestingly, there is no HF addition by-products with double bond formed. It is worth to point out that NMR yields are reported for some acyl fluorides with high volatility (2d, 2f, 2n, 2u) or unstablility upon purification (2o, 2v, 2z). Furthermore, another attractive feature of this protocol is illustrated by readily scale-up synthesis of 2a, a good anhydrous fluorine source for effective SNAr fluorination [27], on 5 mmol scale with a good isolated yield of the target product, thus demonstrating good scalability of the transformation.
2c 59%
H 2N
2o (38%)
2n (59%)
2p (0%)
Aliphatic or cinnamic carboxylic acids O O F
6
O
O F
10
2q 77% (93%)
F F
14 2s 35%
2r 80%
F
O
O
O O
O F
H
Cl
O 2v (86%)
2u (65%)
O F
O
O
O
F F
2z (69%)
F
O
O MeO
2dd 42%
2cc 52% (70%)
F
2ee 63%
O
O
Cl 2bb 55%
2aa 53%
F
O 2N
2x 75%
O
F
2y 20% (56%) O
F
O
H O
2w 74%
O O
O
H
F
2t 74%
O
F
Cl
F
2ff 47% O
F
O Ph
O
O
F
Cl 2gg 29%
2hh 66%
O
F 2ii 44%
2jj 45%
Standard reaction conditions: carboxylic acid (1, 0.4 mmol), Cu(O2CCF2SO2F)2 (0.8 mmol) in MeCN (4 mL) under Ar atmosphere at room temperature for 15 min. Yields of isolated products are given. Yields in parentheses were determined by 19F NMR spectroscopy using trifluorotoluene as an internal standard. a
To illustrate the synthetic application of acyl fluorides synthesized, further transformation of the acyl fluoride products was preliminarily investigated. As revealed in Scheme 3, the reactions of acyl fluoride 2a with either PhCH2NH2, pbromophenol, or PhCH2SH efficiently produced the corresponding amide 3 and esters 4 and 5 in excellent yields.
Additionally, the palladium/copper-catalyzed direct acylation of azoles with acyl fluoride 2a was carried out for the facile generation of ketone 6. All these examples demonstrate the diverse reactivity and application of valuable acyl fluorides.
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments O
PhCH2NH2 DIPEA, MeCN, rt
N H MeO
(A)
(B)
3 96%
O MeO Br
O
2a (C)
O MeO
F
p-bromophenol NEt3, DMF, rt
The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (Nos. 21421002, 21871283, 21737004, 21672239).
O
PhCH2SH NEt3, DMF, rt
S
MeO 5-phenyloxazole Pd(PPh3)4 (cat.), CuCl/PPh3 (cat.) K2CO3, toluene, 80 oC
4 91% N
O
Appendix A. Supplementary data
O
(D) 6 56%
5 99%
OMe
Scheme 3 Synthetic appliction of acyl flouride 2a
Supplementarymaterial relatedtothis article can be found, in the online version, at doi: References [1] C. S. Schindler, P. M. Forster, E. M. Carreira, Org. Lett. 12 (2010) 4102-4105.
With respect with the reaction mechanism, we suggest the following mechanistic pathway shown in Scheme 4. Carboxylic acids react with Cu(O2CCF2SO2F)2 to afford the reaction intermediate [A] and fluoride ion. The subsequent nucleophilic attack of fluoride ion at the carbonyl group of intermediate [A] finishes the desired acyl fluoride products. Notably, coordination of copper cation in the reaction system with carbonyl group of intermediate [A] may play an important role in the subsequent nucleophilic reaction since replacement of Cu(O2CCF2SO2F)2 with FSO2CF2COOMe results in no formation of the desired acyl product. It should be mentioned that the formation of difluorocarbene and CF3 ion via the decomposition of Cu(O2CCF2SO2F)2 occurs during the reactions, which might result in the use of more amounts of Cu(O2CCF2SO2F)2 as a
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Cu2+
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OH
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OSO2CF2COO F
R
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O
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O
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2+ + O3SCF2COO Cu
[A]
Scheme 4 Proposed mechanistic pathway for acyl fluoride synthesis from carboxylic acids with Cu(O2CCF2SO2F)2
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Declaration of interests
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China b
School of Chemical Engineering and Food Science, Zhengzhou Institute of Technology, 18 Yingcai Street, Zhengzhou, 450044, China c
*E-mail: [email protected]; [email protected] # These authors contributed equally.
☒ The authors declare that they have no known
competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:
Cu(O2CCF2SO2F)2
O R
OH
MeCN, rt, 15 min
O R
F
35 examples
A simple, rapid and efficient acyl fluoride synthesis from inexpensive carboxylic acids with Cu(O2CCF2SO2F)2 as a deoxofluorination reagent, previously used as a good trifluoromethylating reagent, has been developed.
[75]
Highlights
Rapid synthesis of acryl fluorides from
[74]
carboxylic acids
Graphical Abstract
reagent instead of
Rapid Synthesis of Acyl Fluorides from Carboxylic Acids with Cu(O2CCF2SO2F)2 Bingjun Le,a ,# Hao Wu,b,# Xiaojun Hu,*a Xiumiao Zhou,c Yong Guo,b Qing-Yun Chen,b Chao Liu*a,b
Cu(O2CCF2SO2F)2 as
a
deoxofluorination
a trifluoromethylating
reagent
Capable of versatile derivatization and latestage functionalization
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