A general palladium-catalyzed carbonylative synthesis of α-CF3-substituted ketones and carboxylic acid derivatives

doi:10.1016/S1872-2067(23)64623-6

Abstract

Abstract:

α-CF₃-substituted carboxylic acid derivatives have drawn wide attention owing to their importance for both pharmaceutical and synthetic communities. However, methodologies for their construction are still very limited. Herein, we developed a general palladium-catalyzed carbonylative procedure for the synthesis of α-CF₃-substituted ketones and carboxylic acid derivatives. With amines, phenols, alcohols, arylboronic acids, and even less-nucleophilic sulfonamides and amides as the reaction partners, the corresponding amides, esters, ketones and imides were obtained in good yields with excellent functional group tolerance. Furthermore, this protocol has also been applied to the late-stage modification of 25 densely functionalized pharmaceutical agents and natural products.

Key words: α-Trifluoromethyl substituted amide, Esters, Ketone, Imide, Carbonylation

Zhi-Peng Bao, Nai-Xian Sun, Xiao-Feng Wu. A general palladium-catalyzed carbonylative synthesis of α-CF₃-substituted ketones and carboxylic acid derivatives[J]. Chinese Journal of Catalysis, 2024, 60: 171-177.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64623-6

https://www.cjcatal.com/EN/Y2024/V60/I5/171

Figures/Tables 7

Fig. 1. Selected examples of bioactive α-CF3 substituted carboxylic acid derivatives.

Fig. 2. Methodologies for the synthesis of α-CF3-substituted carbonyl compounds.

Table 1 Optimization of the reaction conditions a.

Entry	Catalyst/Ligand	Base	Yield^b (%)
1	Pd(OAc)₂/PPh₃	Na₂CO₃	38
2	Pd(acac)₂/PPh₃	Na₂CO₃	42
3	PdI₂/PPh₃	Na₂CO₃	43
4	PdI₂/TFP	Na₂CO₃	38
5	PdI₂/DPEphos	Na₂CO₃	51
6	PdI₂/Sphos	Na₂CO₃	56
7	PdI₂/Xphos	Na₂CO₃	13
8	PdI₂/Ruphos	Na₂CO₃	34
9	PdI₂/Sphos	Na₂CO₃	47
10	PdI₂/Sphos	K₂CO₃	52
11	PdI₂/Sphos	Cs₂CO₃	38
12	PdI₂/Sphos	NEt₃	64
13	PdI₂/Sphos	DiPEA	78
14^c	PdI₂/Sphos	DiPEA	82
15^c,d	PdI₂/Sphos	DiPEA	60
16^c,e	PdI₂/Sphos	DiPEA	51

Fig. 3. Substrate scope of amines, phenols, alcohols, arylboronic acids and trifluoromethylated secondary alkyl iodides. a Reaction conditions: 1a (0.3 mmol), 2 (2.5 equiv.), PdI2 (5 mol%), Sphos (11 mol%), DiPEA (1.5 equiv.), CO (20 bar), MeCN (1.5 mL), 80 °C for 24 h, isolated yield. b Arylboronic acids (0.3 mmol), 2a (3 equiv.), PdI2 (2.5 mol%), Sphos (6 mol%), K2CO3 (1.5 equiv.), CO (20 bar), PhCF3 (1.5 mL), H2O (20 μL), 80 °C for 24 h. c 0.15 mmol scale.

Fig. 4. Late-stage trifluoropropionylation of densely functionalized pharmaceutical agents and natural products. a Reaction conditions: nucleophiles (0.3 mmol), 2-Iodo-1,1,1-trifluoroethane (0.75 mmol), PdI2 (5 mol%), Sphos (11 mol%), DiPEA (0.45 mmol), CO (20 bar), MeCN (1.5 mL), 80 °C for 24 h, isolated yield. b DiPEA (0.75 mmol), the corresponding amine hydrochloride salts were used.

Fig. 5. (A) Less-nucleophilic reagents. (B) Scale-up preparation and synthetic transformation. (C) Competition between N-nucleophile and O-nucleophile under standard condition. (D) Radical inhibition experiments. (E) Radical capture experiment.

Fig. 6. Proposed mechanism.

References

[1]	S. Purser, P. R. Moore, S. Swallow, V. Gouverneur, Chem. Soc. Rev., 2008, 37, 320-330.
[2]	C. Alonso, E. Martinez de Marigorta, G. Rubiales, F. Palacios, Chem. Rev., 2015, 115, 1847-1935.
[3]	J. Charpentier, N. Fruh, A. Togni, Chem. Rev., 2015, 115, 650-682.
[4]	D. A. Nagib, M. E. Scott, D. W. C. MacMillan, J. Am. Chem. Soc., 2009, 131, 10875-10877.
[5]	D. S. Wishart, Y. D. Feunang, A. C. Guo, E. J. Lo, A. Marcu, J. R. Grant, T. Sajed, D. Johnson, C. Li, Z. Sayeeda, N. Assempour, I. Iynkkaran, Y. Liu, A. Maciejewski, N. Gale, A. Wilson, L. Chin, R. Cummings, D. Le, A. Pon, C. Knox, M. Wilson, Nucleic Acids Res., 2018, 46, D1074-D1082.
[6]	F.-P. Wu, Y. Yuan, X.-F. Wu, Angew. Chem. Int. Ed., 2021, 60, 25787-25792.
[7]	C. P. Mavragani, H. M. Moutsopoulos, J. Autoimmunity, 2020, 110, 102364.
[8]	S.-H. Lu, T. Yamagata, K. Atsuki, L. Sun, C. P. Smith, N. Yoshimura, M. B. Chancellor, W. C. de Groat, Brain Res., 2002, 946, 72-78.
[9]	C.-P. Zhang, Z.-L. Wang, Q.-Y. Chen, C.-T. Zhang, Y.-C. Gu, J.-C. Xiao, Chem. Commun., 2011, 47, 6632-6634.
[10]	W.-X. Lv, Y.-F. Zeng, Q. Li, Y. Chen, D.-H. Tan, L. Yang, H. Wang, Angew. Chem. Int. Ed., 2016, 55, 10069-10073.
[11]	R. Tomita, Y. Yasu, T. Koike, M. Akita, Angew. Chem. Int. Ed., 2014, 53, 7144-7148.
[12]	Y.-B. Wu, G.-P. Lu, T. Yuan, Z.-B. Xu, L. Wan, C. Cai, Chem. Commun., 2016, 52, 13668-13670.
[13]	Z. He, R. Zhang, M. Hu, L. Li, C. Ni, J. Hu, Chem. Sci., 2013, 4, 3478-3483.
[14]	B. Morandi, E. M. Carreira, Angew. Chem. Int. Ed., 2011, 50, 9085-9088.
[15]	Y. R. Malpani, B. K. Biswas, H. S. Han, Y.-S. Jung, S. B. Han, Org. Lett., 2018, 20, 1693-1697.
[16]	K. Miura, M. Taniguchi, K. Nozaki, K. Oshima, K. Utimoto, Tetrahedron Lett., 1990, 31, 6391-6394.
[17]	Y. Itoh, K. Mikami, Org. Lett., 2005, 7, 649-651.
[18]	K. Mikami, Y. Tomita, Y. Ichikawa, K. Amikura, Y. Itoh, Org. Lett., 2006, 8, 4671-4673.
[19]	K. Sato, T. Yuki, R. Yamaguchi, T. Hamano, A. Tarui, M. Omote, I. Kumadaki, A. Ando, J. Org. Chem., 2009, 74, 3815-3819.
[20]	V. Matousek, A. Togni, V. Bizet, D. Cahard, Org. Lett., 2011, 13, 5762-5765.
[21]	T. Kawamoto, R. Sasaki, A. Kamimura, Angew. Chem. Int. Ed., 2017, 56, 1342-1345.
[22]	X. Su, H. Huang, Y. Yuan, Y. Li, Angew. Chem. Int. Ed., 2017, 56, 1338-1341.
[23]	H. Wang, W. Shi, Y. Li, M. Yu, Y. Gao, A. Lei, CCS Chem., 2020, 3, 1710-1717.
[24]	P. V. Pham, D. A. Nagib, D. W. C. MacMillan, Angew. Chem. Int. Ed., 2011, 50, 6119-6122.
[25]	S. Das, A. S. K. Hashmi, T. Schaub, Adv. Synth. Catal., 2018, 361, 720-724.
[26]	P. Novák, A. Lishchynskyi, V. V. Grushin, J. Am. Chem. Soc., 2012, 134, 16167-16170.
[27]	J. Wu, H. Wu, X. Liu, Y. Zhang, G. Huang, C. Zhang, Org. Lett., 2022, 24, 4322-4327
[28]	D. Lin, Y. Chen, Z. Dong, P. Pei, H. Ji, L. Tai, L.-A. Chen, CCS Chem., 2023, 5, 1386-1397.
[29]	X. Yu, A. Maity, A. Studer, Angew. Chem. Int. Ed., 2023, 62, e202310288.
[30]	H.-J. Ai, Y. Yuan, X.-F. Wu. Chem. Sci., 2022, 13, 2481-2486.
[31]	Z. Long, Z. Wang, D. Zhou, D. Wan, J. You, Org. Lett., 2017, 19, 2777-2780.
[32]	H. E. Bartrum, D. C. Blakemore, C. J. Moody, C. J. Hayes, Chem. Eur. J., 2011, 17, 9586-9589.
[33]	Z.-P. Bao, X. F. Wu, Angew. Chem. Int. Ed., 2023, 62, e202301671.
[34]	H. Y. Zhao, Z. Feng, Z. Luo, X. Zhang, Angew. Chem. Int. Ed., 2016, 55, 10401-10405.
[35]	T. L. Andersen, M. W. Frederiksen, K. Domino, T. Skrydstrup, Angew. Chem. Int. Ed., 2016, 55, 10396-10400.
[36]	R. Cheng, H.-Y. Zhao, S. Zhang, X. Zhang, ACS Catal., 2020, 10, 36-42.
[37]	H. Yin, J. J. Kumke, K. Domino, T. Skrydstrup, ACS. Catal., 2018, 8, 3853-3858.
[38]	S. Sumino, A. Fusano, T. Fukuyama, I. Ryu, Acc. Chem. Res., 2014, 47, 1563-1574.
[39]	Q. Liu, H. Zhang, A. Lei, Angew. Chem. Int. Ed., 2011, 50, 10788-10799.
[40]	L. Zeng, H. Li, J. Hu, D. Zhang, J. Hu, P. Peng, S. Wang, R. Shi, J. Peng, C.-W. Pao, J.-L. Chen, J.-F. Lee, H. Zhang, Y.-H. Chen, A. Lei, Nat. Catal., 2020, 3, 438-445.

A general palladium-catalyzed carbonylative synthesis of α-CF₃-substituted ketones and carboxylic acid derivatives

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 7

References

Related Articles 15

Recommended Articles

Metrics

[1]	Ke Huang, Shicheng Yuan, Rongyan Mei, Ge Yang, Peng Bai, Hailing Guo, Chunzheng Wang, Svetlana Mintova. Mo-promoted Pd/NaY catalyst for indirect oxidative carbonylation of methanol to dimethyl carbonate [J]. Chinese Journal of Catalysis, 2024, 60(5): 327-336.
[2]	Xingju Li, Zheng Li, Siquan Feng, Xiangen Song, Li Yan, Jiali Mu, Qiao Yuan, Lili Ning, Weimiao Chen, Zhongkang Han, Yunjie Ding. Promotional role of Ag₁ on Pd₁ in dual-site configurations from atomic dispersion of alloy nanoparticles for alkyne dialkoxycarbonylation [J]. Chinese Journal of Catalysis, 2024, 59(4): 282-292.
[3]	Yu-Shuai Xu, Hong-Hui Wang, Qi-Yuan Li, Shi-Nan Zhang, Si-Yuan Xia, Dong Xu, Wei-Wei Lei, Jie-Sheng Chen, Xin-Hao Li. Functional ladder-like heterojunctions of Mo₂C layers inside carbon sheaths for efficient CO₂ fixation [J]. Chinese Journal of Catalysis, 2024, 58(3): 138-145.
[4]	Yaejun Baik, Kyeongjin Lee, Minkee Choi. Catalytic conversion of triglycerides into diesel, jet fuel, and lube base oil [J]. Chinese Journal of Catalysis, 2024, 58(3): 15-24.
[5]	Yucheng Jin, Xiaolin Liu, Chen Qu, Changjun Li, Hailong Wang, Xiaoning Zhan, Xinyi Cao, Xiaofeng Li, Baoqiu Yu, Qi Zhang, Dongdong Qi, Jianzhuang Jiang. Perylene diimide covalent organic frameworks super-reductant for visible light-driven reduction of aryl halides [J]. Chinese Journal of Catalysis, 2024, 57(2): 171-183.
[6]	Changpo Ma, Ying Lai, Tiange Zhao, Xiaoxuan Zhang, Haichao Liu, Weiran Yang. Direct synthesis of α,ω-dicarboxylic acids via dicarbonylation of cyclic ethers [J]. Chinese Journal of Catalysis, 2024, 56(1): 122-129.
[7]	Abhishek R. Varma, Bhushan S. Shrirame, Sunil K. Maity, Deepti Agrawal, Naglis Malys, Leonardo Rios-Solis, Gopalakrishnan Kumar, Vinod Kumar. Recent advances in fermentative production of C4 diols and their chemo-catalytic upgrading to high-value chemicals [J]. Chinese Journal of Catalysis, 2023, 52(9): 99-126.
[8]	Huizhen Li, Yanlei Chen, Qing Niu, Xiaofeng Wang, Zheyuan Liu, Jinhong Bi, Yan Yu, Liuyi Li. The crystalline linear polyimide with oriented photogenerated electron delivery powering CO₂ reduction [J]. Chinese Journal of Catalysis, 2023, 49(6): 152-159.
[9]	Xing-Wei Gu, Youcan Zhang, Fengqian Zhao, Han-Jun Ai, Xiao-Feng Wu. Phosphine-catalyzed photo-induced alkoxycarbonylation of alkyl iodides with phenols and 1,4-dioxane through charge-transfer complex [J]. Chinese Journal of Catalysis, 2023, 48(5): 214-223.
[10]	Han-Jun Ai, Fengqian Zhao, Xiao-Feng Wu. SET or TET? Iron-catalyzed aminocarbonylation of unactivated alkyl halides with amines, amides, and indoles via a substrate dependent mechanism [J]. Chinese Journal of Catalysis, 2023, 47(4): 121-128.
[11]	Shu-Mei Xia, Zhi-Wen Yang, Kai-Hong Chen, Ning Wang, Liang-Nian He. Efficient hydrocarboxylation of alkynes based on carbodiimide-regulated in situ CO generation from HCOOH: An alternative indirect utilization of CO₂ [J]. Chinese Journal of Catalysis, 2022, 43(7): 1642-1651.
[12]	Kaiyi Su, Chaofeng Zhang, Yehong Wang, Jian Zhang, Qiang Guo, Zhuyan Gao, Feng Wang. Unveiling the highly disordered NbO₆ units as electron-transfer sites in Nb₂O₅ photocatalysis with N-hydroxyphthalimide under visible light irradiation [J]. Chinese Journal of Catalysis, 2022, 43(7): 1894-1905.
[13]	Yangrui Xu, Xiaodie Zhu, Huan Yan, Panpan Wang, Minshan Song, Changchang Ma, Ziran Chen, Jinyu Chu, Xinlin Liu, Ziyang Lu. Hydrochloric acid-mediated synthesis of ZnFe₂O₄ small particle decorated one-dimensional Perylene Diimide S-scheme heterojunction with excellent photocatalytic ability [J]. Chinese Journal of Catalysis, 2022, 43(4): 1111-1122.
[14]	Zizhan Liang, Rongchen Shen, Peng Zhang, Youji Li, Neng Li, Xin Li. All-organic covalent organic frameworks/perylene diimide urea polymer S-scheme photocatalyst for boosted H₂ generation [J]. Chinese Journal of Catalysis, 2022, 43(10): 2581-2591.
[15]	Kaipeng Cao, Dong Fan, Shu Zeng, Benhan Fan, Nan Chen, Mingbin Gao, Dali Zhu, Linying Wang, Peng Tian, Zhongmin Liu. Organic-free synthesis of MOR nanoassemblies with excellent DME carbonylation performance [J]. Chinese Journal of Catalysis, 2021, 42(9): 1468-1477.