Mechanochemical Synthesis of Diarylethynes from Aryl Iodides and CaC2

Pit van Bonn; Carsten Bolm

doi:10.1055/a-1733-6254

Synlett, Table of Contents

Synlett 2022; 33(09): 893-897
DOI: 10.1055/a-1733-6254

cluster

Mechanochemical Synthesis of Diarylethynes from Aryl Iodides and CaC₂

Pit van Bonn

,

Carsten Bolm ∗

Abstract

All articles of this category

Abstract

A mechanochemical synthesis of diarylethynes from aryl iodides and calcium carbide as acetylene source is reported. The reaction is catalyzed by a palladium catalyst in the presence of copper salt, base, and ethanol as liquid assisting grinding (LAG) additive. Various aryl and heteroaryl iodides have been converted in up to excellent yields.

Key words

mechanochemistry - calcium carbide - ball milling - diarylethyne - catalysis - palladium

Full Text

References

References and Notes

1a Ostwald W. Lehrbuch der Allgemeinen Chemie . Engelmann; Leipzig: 1887
1b Ostwald W. Handbuch der Allgemeinen Chemie . Akademische Verlagsgesellschaft; Leipzig: 1919

2a James SL, Adams CJ, Bolm C, Braga D, Collier P, Friščić T, Grepioni F, Harris KD. M, Hyett G, Jones W, Krebs A, Mack J, Maini L, Orpen AG, Parkin IP, Shearouse WC, Steed JW, Waddell DC. Chem. Soc. Rev. 2012; 41: 413
2b Do J.-L, Friščić T. ACS Cent. Sci. 2017; 3: 13
2c Howard JL, Cao Q, Browne DL. Chem. Sci. 2018; 9: 3080
2d Friščić T, Mottillo C, Titi HM. Angew. Chem. Int. Ed. 2020; 59: 1018
2e Pickhardt W, Grätz S, Borchardt L. Chem. Eur. J. 2020; 26: 12903
2f Ardila-Fierro KJ, Hernández JG. ChemSusChem 2021; 14: 2145
2g Hernandez JG, Bolm C. J. Org. Chem. 2017; 82: 4007
2h Porcheddu A, Colacino E, De Luca L, Delogu F. ACS Catal. 2020; 10: 8344
2i Zhu S.-E, Li F, Wang G.-W. Chem. Soc. Rev. 2013; 42: 7535
2j Wang GW. Chin. J. Chem. 2021; 39: 1797
2k Kaiser RP, Krake EF, Backer L, Urlaub J, Baumann W, Handler N, Buschmann H, Beweries T, Holzgrabe U, Bolm C. Chem. Commun. 2021; 57: 11956

3 Kubota K, Ito H. Trends Chem. 2020; 2: 1066
4 Fulmer DA, Shearouse WC, Medonza ST, Mack J. Green Chem. 2009; 11: 1821
5 Thorwirth R, Stolle A, Ondruschka B. Green Chem. 2010; 12: 985

6a Deng D, Huang D, Sun X, Gao B. Synthesis 2021; 53: 3522
6b Mei H, Yin Z, Liu J, Sun H, Han J. Chin. J. Chem. 2019; 37: 292
6c Koike T, Akita M. Acc. Chem. Res. 2016; 49: 1937
6d Shimizu Y, Kanai M. Tetrahedron Lett. 2014; 55: 3727
6e Huang M.-H, Hao W.-J, Li G, Tu S.-J, Jiang B. Chem. Commun. 2018; 54: 10791

7a Sonogashira K, Tohda Y, Hagihara N. Tetrahedron Lett. 1975; 4467
7b Pal M, Kundu NG. J. Chem. Soc., Perkin Trans. 1 1996; 449
7c Li C.-J, Chen D.-L, Costello CW. Org. Process Res. Dev. 1997; 1: 325

8 For a general review on the use of acetylene, see: Trotus I.-T, Zimmermann T, Schüth F. Chem. Rev. 2014; 114: 1761

9a Rodygin KS, Ledovskaya MS, Voronin VV, Lotsman KA, Ananikov VP. Eur. J. Org. Chem. 2021; 43
9b Voronin VV, Ledovskaya MS, Bogachenkov AS, Rodygin KS, Ananikov VP. Molecules 2018; 23: 2442
9c Rodygin KS, Werner G, Kucherov FA, Ananikov VP. Chem. Asian J. 2016; 11: 965

10 Zhang W, Wu H, Liu Z, Zhong P, Zhang L, Huang X, Cheng J. Chem. Commun. 2006; 4826

11a Chuentragool P, Vongnam K, Rashatasakhon P, Sukwattanasinitt M, Wacharasindhu S. Tetrahedron 2011; 67: 8177
11b Thavornsin N, Sukwattanasinitt M, Wacharasindhu S. Polym. Chem. 2014; 5: 48
11c Matake R, Niwa Y, Matsubara H. Org. Lett. 2015; 17: 2354
11d Fu R, Li Z. Eur. J. Org. Chem. 2017; 6648
11e Hosseini A, Pilevar A, Hogan E, Mogwitz B, Schulze AS, Schreiner PR. Org. Biomol. Chem. 2017; 15: 6800
11f Li Z, Ma X. Synlett 2021; 32: 631

12a Turberg M, Ardila-Fierro KJ, Bolm C, Hernandez JG. Angew. Chem. Int. Ed. 2018; 57: 10718
12b Li A, Song H, Xu X, Meng H, Lu Y, Li C. ACS Sustainable Chem. Eng. 2018; 6: 9560
12c Ardila-Fierro KJ, Bolm C, Hernandez JG. Angew. Chem. Int. Ed. 2019; 58: 12945
12d Casco ME, Kirchhoff S, Leistenschneider D, Rauche M, Brunner E, Borchardt L. Nanoscale 2019; 11: 4712
12e Hosseini A, Schreiner PR. Eur. J. Org. Chem. 2020; 4339
12f Li Y, Li S, Xu X, Gu J, He X, Meng H, Lu Y, Li C. ACS Sustainable Chem. Eng. 2021; 9: 9221

For recent reviews on liquid-assisted grinding (LAG), see:

13a Ying P, Yu J, Su W. Adv. Synth. Catal. 2021; 363: 1246
13b Bowmaker GA. Chem. Commun. 2013; 49: 334
13c Friščić T, Childs SL, Rizvi SA. A, Jones W. CrystEngComm 2009; 11: 418

14 1,2-Di-p-tolylethyne (2a); Procedure: A stainless steel milling jar (volume: 5 mL) equipped with one stainless steel milling ball (diameter: 10 mm) was loaded with Pd(OAc)₂ (2.3 mg, 0.01 mmol, 5 mol%), PPh₃ (5.3 mg, 0.02 mmol, 10 mol%), CuI (3.8 mg, 0.02 mmol, 10 mol%), K₂CO₃ (55.3 mg, 0.4 mmol, 2.0 equiv) and iodo-4-methylbenzene (87.2 mg, 0.4 mmol, 2.0 equiv). The jar was brought inside a glovebox and CaC₂ [25.6 mg, 0.4 mmol, 2.0 equiv of technical grade CaC₂ (75.54% purity), real amount added 0.30 mmol] and ethanol (45 μL) were added. The jar was closed tightly under argon atmosphere using Teflon tape for the thread and additional Parafilm was wrapped around the closed jar. After 90 min at 30 Hz the jar was opened in air, the product was extracted with ethyl acetate (5 × 3 mL) and evaporated on silica. The product was purified by flash column chromatography on silica gel [n-pentane; R_f 0.39 (n-pentane)] to give 1,2-di-p-tolylethyne (40.1 mg, 0.194 mmol, 97%) as a pale-yellow solid. ¹H NMR (600 MHz, CDCl₃): δ = 7.43 (d, J = 8.1 Hz, 4 H), 7.16 (d, J = 7.8 Hz, 4 H), 2.38 (s, 6 H) ppm. ¹³C{¹H} NMR (151 MHz, CDCl₃): δ = 138.3, 131.6, 129.2, 120.5, 89.0, 21.6 ppm. The analytic data is consistent with reported data (ref. 11f).
15 When the typical procedure (see ref. 14) was modified by not using the glovebox and adding freshly ground CaC₂ and ethanol in air followed by flushing the jar with argon, 2a was obtained in only 80% yield (as determined by ¹H NMR spectroscopy). Most likely, the moisture sensitivity of CaC₂ and a partial evaporation of ethanol were responsible for this decrease in yield. Also in this case, 2a′ remained undetected.
16 Besides 2i (44% yield), 22% of aryl iodide 1i could be isolated. After the unsuccessful attempt to couple 1-iodonaphthalene, the starting material was recovered in 58%. Except when detailed, no mono-aryl alkynes were observed in any of the couplings.
17 After our submission, Ito, Kubota, and co-workers reported a mechanochemical Sonogashira cross-coupling of aryl bromides and chlorides with triisopropylsilyl acetylene and aryl acetylenes under high-temperature ball-milling conditions. The protocol expands the scope of the mechanochemical Sonogashira cross-couplings developed by Mack and Stolle and highlights the benefits of ball milling compared to solution-based reactions of poorly soluble substrates. See: Gao Y, Feng C, Seo T, Kubota K, Ito H. Chem. Sci. 2021; 13: 430

Supplementary Material

Supporting Information