Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2020; 31(07): 713-717
DOI: 10.1055/s-0039-1691590
DOI: 10.1055/s-0039-1691590
letter
Difluorocarbene-Based Cyanation of Aryl Iodides
The authors thank the National Natural Science Foundation (21421002, 21672242, 21971252), the Key Research Program of Frontier Sciences, Chinese Academy of Sciences (CAS) (QYZDJSSW-SLH049), the Youth Innovation Promotion Association CAS (2019256), the Fujian Institute of Innovation, CAS (FJCXY18040102), the Shanghai Research Institute of Chemical Industry Co., Ltd. (SKL-LCTP-201802), the Hunan Provincial Hengyang City Joint Fund Project (2018JJ4036), the general project of the University of South China (18C0438), the Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study (0223-0007-000004), and the Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, CAS (2018-10) for financial support.Further Information
Publication History
Received: 15 January 2020
Accepted after revision: 15 January 2020
Publication Date:
03 February 2020 (online)
◊ These authors contributed equally to this work.
Abstract
A large number of efficient cyanation methods have been developed because of the wide range of applications of nitriles, but conventional methods usually suffer from the need for a toxic cyanation reagent. Although difluorocarbene chemistry has received increasing attention, the use of difluorocarbene as a sources of the nitrile carbon for nitrile groups remains largely unexplored. We describe a difluorocarbene-based cyanation of aryl iodides promoted by a cheap copper source, Cu(NO3)2·2.5H2O, under an air atmosphere. Ph3P+CF2CO2 –, an easily available and shelf-stable difluorocarbene reagent, and NaNH2 are used as the carbon source and the nitrogen source for the nitrile group, respectively. The cyanation protocol is attractive because no toxic reagent is used and performing the reactions under an air atmosphere is operationally convenient.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1691590.
- Supporting Information
-
References and Notes
- 1a The Chemistry of the Cyano Group . Rappoport Z. Wiley Interscience; London: 1970
- 1b Fatiadi A. In Triple-Bonded Functional Groups, Vol. 2. Patai P, Rappaport Z. Wiley; Chichester: 1983: 1057
- 1c Jones LH, Summerhill NW, Swain NA, Mills JE. MedChemComm 2010; 1: 309
- 2a Wen Q, Jin J, Zhang L, Luo Y, Lu P, Wang Y. Tetrahedron Lett. 2014; 55: 1271
- 2b Pellissier H. Adv. Synth. Catal. 2015; 357: 857
- 2c Kurono N, Ohkuma T. ACS Catal. 2016; 6: 989
- 2d Schörgenhumer J, Waser M. Org. Chem. Front. 2016; 3: 1535
- 2e Yu J.-T, Teng F, Cheng J. Adv. Synth. Catal. 2017; 359: 26
- 2f Yan G, Zhang Y, Wang J. Adv. Synth. Catal. 2017; 359: 4068
- 2g Chaitanya M, Anbarasan P. Org. Biomol. Chem. 2018; 16: 7084
- 2h Cui J, Song J, Liu Q, Liu H, Dong Y. Chem. Asian J. 2018; 13: 482
- 3a Zhang W, Wang F, McCann SD, Wang D, Chen P, Stahl SS, Liu G. Science 2016; 353: 1014
- 3b Wang D, Zhu N, Chen P, Lin Z, Liu G. J. Am. Chem. Soc. 2017; 139: 15632
- 3c Li J, Zhang Z, Wu L, Zhang W, Chen P, Lin Z, Liu G. Nature 2019; 574: 516
- 4a Anderson BA, Bell EC, Ginah FO, Harn NK, Pagh LM, Wepsiec JP. J. Org. Chem. 1998; 63: 8224
- 4b Yang C, Williams JM. Org. Lett. 2004; 6: 2837
- 5a Hoffmann HM. R, Iranshahi L. J. Org. Chem. 1984; 49: 1174
- 5b Sakamoto T, Ohsawa K. J. Chem. Soc., Perkin Trans. 1 1999; 2323
- 6a Kaupp G, Schmeyers J, Boy J. Chem. Eur. J. 1998; 4: 2467
- 6b Okamoto K, Watanabe M, Murai M, Hatano R, Ohe K. Chem. Commun. 2012; 48: 3127
- 7a Hughes TV, Hammond SD, Cava MP. J. Org. Chem. 1998; 63: 401
- 7b Anbarasan P, Neumann H, Beller M. Chem. Eur. J. 2011; 17: 4217
- 7c Cai Y, Qian X, Rérat A, Auffrant A, Gosmini C. Adv. Synth. Catal. 2015; 357: 3419
- 7d Kiyokawa K, Nagata T, Minakata S. Angew. Chem. Int. Ed. 2016; 55: 10458
- 8a Zhdankin VV, Kuehl CJ, Krasutsky AP, Bolz JT, Mismash B, Woodward JK, Simonsen AJ. Tetrahedron Lett. 1995; 36: 7975
- 8b Ma B, Lin X, Lin L, Feng X, Liu X. J. Org. Chem. 2017; 82: 701
- 8c Nagata T, Matsubara H, Kiyokawa K, Minakata S. Org. Lett. 2017; 19: 4672
- 8d Le Vaillant F, Wodrich MD, Waser J. Chem. Sci. 2017; 8: 1790
- 8e Declas N, Le Vaillant F, Waser J. Org. Lett. 2019; 21: 524
- 9a Talavera G, Peña J, Alcarazo M. J. Am. Chem. Soc. 2015; 137: 8704
- 9b Barrado AG, Zieliński A, Goddard R, Alcarazo M. Angew. Chem. Int. Ed. 2017; 56: 13401
- 9c Li X, Golz C, Alcarazo M. Angew. Chem. Int. Ed. 2019; 58: 9496
- 10a Kou X, Zhao M, Qiao X, Zhu Y, Tong X, Shen Z. Chem. Eur. J. 2013; 19: 16880
- 10b Zhu Y, Li L, Shen Z. Chem. Eur. J. 2015; 21: 13246
- 10c Zhu Y, Zhao M, Lu W, Li L, Shen Z. Org. Lett. 2015; 17: 2602
- 11a Ding S, Jiao N. J. Am. Chem. Soc. 2011; 133: 12374
- 11b Kim J, Choi J, Shin K, Chang S. J. Am. Chem. Soc. 2012; 134: 2528
- 11c Pawar AB, Chang S. Chem. Commun. 2014; 50: 448
- 12a Ren X, Chen J, Chen F, Cheng J. Chem. Commun. 2011; 47: 6725
- 12b Zheng K, Liu B, Chen S, Chen F. Tetrahedron Lett. 2013; 54: 5250
- 13a Bag S, Jayarajan R, Dutta U, Chowdhury R, Mondal R, Maiti D. Angew. Chem. Int. Ed. 2017; 56: 12538
- 13b McManus JB, Nicewicz DA. J. Am. Chem. Soc. 2017; 139: 2880
- 13c Wang L, Wang G, Zhang J, Bian C, Meng X, Xiao F.-S. Nat. Commun. 2017; 8: 15240
- 13d Gao D.-W, Vinogradova EV, Nimmagadda SK, Medina JM, Xiao Y, Suciu RM, Cravatt BF, Engle KM. J. Am. Chem. Soc. 2018; 140: 8069
- 13e Lennox AJ. J, Goes SL, Webster MP, Koolman HF, Djuric SW, Stahl SS. J. Am. Chem. Soc. 2018; 140: 11227
- 13f Wang X, Studer A. Angew. Chem. Int. Ed. 2018; 57: 11792
- 13g Wang H, Dong Y, Zheng C, Sandoval CA, Wang X, Makha M, Li Y. Chem 2018; 4: 2883
- 13h Lu F.-D, Liu D, Zhu L, Lu L.-Q, Yang Q, Zhou Q.-Q, Wei Y, Lan Y, Xiao W.-J. J. Am. Chem. Soc. 2019; 141: 6167
-
13i
Zhao D,
Xu P,
Ritter T.
Chem 2019; 5: 97
- 14a Anbarasan P, Schareina T, Beller M. Chem. Soc. Rev. 2011; 40: 5049
- 14b Vafaeezadeh M, Hashemi MM, Karbalaie-Reza M. Inorg. Chem. Commun. 2016; 72: 86
- 14c Ushkov AV, Grushin VV. J. Am. Chem. Soc. 2011; 133: 10999
- 14d Senecal TD, Shu W, Buchwald SL. Angew. Chem. Int. Ed. 2013; 52: 10035
- 14e Kristensen SK, Eikeland EZ, Taarning E, Lindhardt AT, Skrydstrup T. Chem. Sci. 2017; 8: 8094
- 15a Zanon J, Klapars A, Buchwald SL. J. Am. Chem. Soc. 2003; 125: 2890
- 15b Jiang Z, Huang Q, Chen S, Long L, Zhou X. Adv. Synth. Catal. 2012; 354: 589
- 15c Kim K, Hong SH. Adv. Synth. Catal. 2017; 359: 2345
- 16a Yu P, Morandi B. Angew. Chem. Int. Ed. 2017; 56: 15693
- 16b Zhang X, Xia A, Chen H, Liu Y. Org. Lett. 2017; 19: 2118
- 16c Yang L, Liu Y.-T, Park Y, Park S.-W, Chang S. ACS Catal. 2019; 9: 3360
- 16d Ueda Y, Tsujimoto N, Yurino T, Tsurugi H, Mashima K. Chem. Sci. 2019; 10: 994
- 17a Rosenmund KW, Struck E. Ber. Dtsch. Chem. Ges. A 1919; 52: 1749
- 17b Ellis GP, Romney-Alexander TM. Chem. Rev. 1987; 87: 779
- 18a Schareina T, Zapf A, Beller M. Chem. Commun. 2004; 1388
- 18b Grossman O, Gelman D. Org. Lett. 2006; 8: 1189
- 19 Chatani N, Hanafusa T. J. Org. Chem. 1986; 51: 4714
- 20 Schareina T, Zapf A, Cotte A, Gotta M, Beller M. Adv. Synth. Catal. 2011; 353: 777
- 21 Zhang G, Ren X, Chen J, Hu M, Cheng J. Org. Lett. 2011; 13: 5004
- 23a Wang F, Zhang W, Zhu J, Li H, Huang K.-W, Hu J. Chem. Commun. 2011; 47: 2411
- 23b Wang F, Luo T, Hu J, Wang Y, Krishnan HS, Jog PV, Ganesh SK, Prakash GK, Olah GA. Angew. Chem. Int. Ed. 2011; 50: 7153
- 23c Li L, Wang F, Ni C, Hu J. Angew. Chem. Int. Ed. 2013; 52: 12390
- 24a Thomoson CS, Dolbier WR. Jr. J. Org. Chem. 2013; 78: 8904
- 24b Xie Q, Ni C, Zhang R, Li L, Rong J, Hu J. Angew. Chem. Int. Ed. 2017; 56: 3206
- 25a Hu M, Ni C, Li L, Han Y, Hu J. J. Am. Chem. Soc. 2015; 137: 14496
- 25b Zheng J, Lin J.-H, Yu L.-Y, Wei Y, Zheng X, Xiao J.-C. Org. Lett. 2015; 17: 6150
- 25c Zhang Z, Yu W, Wu C, Wang C, Zhang Y, Wang J. Angew. Chem. Int. Ed. 2016; 55: 273
- 26a Deng X.-Y, Lin J.-H, Xiao J.-C. Org. Lett. 2016; 18: 4384
- 26b Feng Z, Min Q.-Q, Zhang X. Org. Lett. 2016; 18: 44
- 26c Feng Z, Min QQ, Fu XP, An L, Zhang X. Nat. Chem. 2017; 9: 918
- 26d Fu X.-P, Xue X.-S, Zhang X.-Y, Xiao Y.-L, Zhang S, Guo Y.-L, Leng X, Houk KN, Zhang X. Nat. Chem. 2019; 11: 948
- 27a Zheng J, Cai J, Lin J.-H, Guo Y, Xiao J.-C. Chem. Commun. 2013; 49: 7513
- 27b Deng X.-Y, Lin J.-H, Zheng J, Xiao J.-C. Chem. Commun. 2015; 51: 8805
- 28a Zheng J, Wang L, Lin J.-H, Xiao J.-C, Liang SH. Angew. Chem. Int. Ed. 2015; 54: 13236
- 28b Zheng J, Cheng R, Lin J.-H, Yu DH, Ma L, Jia L, Zhang L, Wang L, Xiao J.-C, Liang SH. Angew. Chem. Int. Ed. 2017; 56: 3196
- 28c Yu J, Lin J.-H, Xiao J.-C. Angew. Chem. Int. Ed. 2017; 56: 16669
- 29 Chen X.-L, Zhou S.-H, Lin J.-H, Deng Q.-H, Xiao J.-C. Chem. Commun. 2019; 55: 1410
- 30 Zhang M, Lin J.-H, Xiao J.-C. Angew. Chem. Int. Ed. 2019; 58: 6079
- 31 Cyanation of Aryl Iodides 1; General Procedure Under air atmosphere, a reaction tube was charged with the appropriate aryl iodide 1 (0.5 mmol), Ph3P+CF2CO2 – (268 mg, 0.75 mmol, 1.5 equiv), ligand L4 (6.3 mg, 5 mol%), Cu(NO3)2·2.5 H2O (143 mg, 0.65 mmol, 1.3 equiv), NaNH2 (39 mg, 1.0 mmol, 2.0 equiv), and anhyd DMF (4 mL). The mixture was stirred at 130 °C for 15 h, then cooled to rt and filtered through a pad of Celite that was washed with CH2Cl2. The combined organic phase was washed with H2O (3 × 15 mL), and the organic layer was further washed with sat. aq Na2SO3 and sat. brine, then dried (Na2SO4) and concentrated under vacuum. The residue was purified by flash column chromatography. 9,9-Dimethyl-9H-fluorene-3-carbonitrile (2k) The reaction was performed on a 0.6 mmol scale. Yellow oil; yield: 85 mg (65%). IR (neat): 3062, 2962, 2924, 2866, 2223, 1609, 1485, 1471, 1447, 1416, 1302, 1283, 1219, 1077, 1023, 893, 835, 783, 759, 737 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.80–7.72 (m, 2 H), 7.69 (s, 1 H), 7.62 (d, J = 7.9 Hz, 1 H), 7.46 (d, J = 7.1 Hz, 1 H), 7.43–7.34 (m, 2 H), 1.48 (s, 6 H). 13C NMR (101 MHz, CDCl3): δ = 154.19, 154.16, 143.8, 137.2, 131.4, 129.1, 127.5, 126.4, 122.9, 121.1, 120.5, 119.7, 110.1, 47.1, 26.8. HRMS (EI); m/z [M]+ calcd for C16H13N: 219.1048; found: 219.1054.
- 32 Shi R, Zhang H, Lu L, Gan P, Sha Y, Zhang H, Liu Q, Beller M, Lei A. Chem. Commun. 2015; 51: 3247