Thiolate-Protected Au25(SC2H4Ph)18 Nanoclusters as a Catalyst for Intermolecular Hydroamination of Terminal Alkynes

Tatsuki Nagata; Yurina Adachi; Yasushi Obora

doi:10.1055/s-0037-1610671

Synlett, Table of Contents

Synlett 2018; 29(20): 2655-2659
DOI: 10.1055/s-0037-1610671

letter

Thiolate-Protected Au₂₅(SC₂H₄Ph)₁₈ Nanoclusters as a Catalyst for Intermolecular Hydroamination of Terminal Alkynes

Tatsuki Nagata

,

Yurina Adachi

,

Yasushi Obora*

Department of Chemistry and Material Engineering, Faculty of Chemistry, Materials and Bioengineering, Kansai University, Suita, Osaka 564-8680, Japan Email: obora@kansai-u.ac.jp

› Author Affiliations

Abstract

All articles of this category

Abstract

Au₂₅(SC₂H₄Ph)₁₈ nanoclusters have high catalytic activity for hydroamination of terminal alkynes. This reaction proceeds under O₂ or air. The presence of molecular oxygen has a profound effect on the Au₂₅(SC₂H₄Ph)₁₈ reactivity. The catalysts can be separated from the mixture after the reaction and reused.

Key words

hydroamination - gold nanocluster - imines - gold catalyst - reusing catalyst

Full Text

References

Reference and Notes

1a Córdova A. Acc. Chem. Res. 2004; 37: 102
1b Nájera C, Sansano JM. Chem. Rev. 2007; 107: 4584
1c Jorgensen KA. Angew. Chem. Int. Ed. 2000; 39: 3558
1d Layer RW. Chem. Rev. 1963; 63: 489
1e Erkkilä A, Majander I, Pihko PM. Chem. Rev. 2007; 107: 5416

2a Gooßen LJ, Huang L, Arndt M, Gooßen K, Heydt H. Chem. Rev. 2015; 115: 2596
2b Müller TE, Hultzsch KC, Yus M, Foubelo F, Tada M. Chem. Rev. 2008; 108: 3795
2c Severin R, Doye S. Chem. Soc. Rev. 2007; 36: 1407
2d Patil RD, Adimurthy S. Asian J. Org. Chem. 2013; 2: 726

3a Chen Q, Lv L, Yu M, Shi Y, Li Y, Pang G, Cao C. RSC Adv. 2013; 3: 18359
3b Tokunaga M, Eckert M, Wakatsuki Y. Angew. Chem. Int. Ed. 1999; 38: 3222
3c Iali W, La Paglia F, Le Goff XF, Sredojević D, Pfeffer M, Djukic JP. Chem. Commun. 2012; 48: 10310
3d Hartung CG, Tillack A, Trauthwein H, Beller M. J. Org. Chem. 2001; 66: 6339
3e Brunet JJ, Chu NC, Diallo O, Vincendeau S. J. Mol. Catal. A: Chem. 2005; 240: 245

4a Gorin DJ, Toste FD. Nature 2007; 446: 395
4b Corma A, Leyva-Pérez A, Sabater MJ. Chem. Rev. 2011; 111: 1657
4c Jia M, Bandini M. ACS Catal. 2015; 5: 1638
4d Ranieri B, Escofet I, Echavarren AM. Org. Biomol. Chem. 2015; 13: 7103
4e Joost M, Amgoune A, Bourissou D. Angew. Chem. Int. Ed. 2015; 54: 15022

5a Mizushima E, Hayashi T, Tanaka M. Org. Lett. 2003; 5: 3349
5b Brouwer C, He C. Angew. Chem. Int. Ed. 2006; 45: 1744

6a Mathew A, Pradeep T. Part. Part. Syst. Charact. 2014; 31: 1017
6b Chakraborty I, Pradeep T. Chem. Rev. 2017; 117: 8208

7a Haruta M, Kobayashi T, Sano H, Yamada N. Chem. Lett. 1987; 16: 405
7b Taketoshi A, Haruta M. Chem. Lett. 2014; 43: 380

8a Tsukuda T. Bull. Chem. Soc. Jpn. 2012; 85: 151
8b Fang J, Zhang B, Yao Q, Yang Y, Xie J, Yan N. Coord. Chem. Rev. 2016; 322: 1
8c Fang J, Zhang B, Yao Q, Yang Y, Xie J, Yan N. Coord. Chem. Rev. 2016; 322: 1

9a Li G, Jin R. Acc. Chem. Res. 2013; 46: 1749
9b Nie X, Qian H, Ge Q, Xu H, Jin R. ACS Nano 2012; 6: 6014
9c Li G, Jiang DE, Liu C, Yu C, Jin R. J. Catal. 2013; 306: 177
9d Li G, Jin R. J. Am. Chem. Soc. 2014; 136: 11347
9e Liu Y, Tsunoyama H, Akita T, Tsukuda T. Chem. Commun. 2010; 46: 550
9f Xie S, Tsunoyama H, Kurashige W, Negishi Y, Tsukuda T. ACS Catal. 2012; 2: 1519

10a Kitahara H, Sakurai H. Chem. Lett. 2010; 39: 46
10b Bobuatong K, Sakurai H, Ehara M. ChemCatChem 2017; 9: 4490

11a Corma A, Concepción P, Domínguez I, Forné V, Sabater MJ. J. Catal. 2007; 251: 39
11b Lee LC, Zhao Y. ACS Catal. 2014; 4: 688
11c Liang S, Hammond L, Xu B, Hammond GB. Adv. Synth. Catal. 2016; 358: 3313

12a Li Q, Das A, Wang S, Chen Y, Jin R. Chem. Commun. 2016; 52: 14298
12b Adachi Y, Kawasaki H, Nagata T, Obora Y. Chem. Lett. 2016; 45: 1457

13a Zhu M, Eckenhoff WT, Pintauer T, Jin R. J. Phys. Chem. 2008; 112: 14221
13b Zhu M, Aikens CM, Hendrich MP, Gupta R, Qian H, Schatz GC, Jin R. J. Am. Chem. Soc. 2009; 131: 2490

14a Okumura M, Kitagawa Y, Haruta M, Yamaguchi K. Appl. Catal., A 2005; 291: 34
14b Roldán A, Ricart JM, Illas F, Pacchioni G. Phys. Chem. Chem. Phys. 2010; 12: 10723
14c Pal R, Wang LM, Pei Y, Wang LS, Zeng XC. J. Am. Chem. Soc. 2012; 134: 9438

15a Zhu Y, Qian H, Jin R. Chem. - A Eur. J. 2010; 16: 11455
15b Zhu Y, Qian H, Zhu M, Jin R. Adv. Mater. 2010; 22: 1915

16a Astruc D, Lu F, Aranzaes JR. Angew. Chem. Int. Ed. 2005; 44: 7852
16b Li MB, Tian SK, Wu Z. Nanoscale 2014; 6: 5714
16c Fujita KI, Fujii A, Sato J, Yasuda H. Synlett 2016; 27: 1941

17a Collins CB, Tofanelli MA, Crook MF, Phillips BD, Ackerson CJ. RSC Adv. 2017; 7: 45061
17b Dreier TA, Ackerson CJ. Angew. Chem. Int. Ed. 2015; 54: 9249
17c Tofanelli MA, Ackerson CJ. J. Am. Chem. Soc. 2012; 134: 16937

18 Preparation of the Au₂₅(SC₂H₄Ph)₁₈ Catalyst The Au₂₅(SC₂H₄Ph)₁₈ nanoclusters were synthesized according to a previously reported method.²⁰ HAuCl₄·4H₂O (2 mmol, 0.8 g) was dissolved in 150 ml tetrahydrofuran (THF) solution containing tetraoctylammonium bromide (2.4 mmol, 1.3 g) at room temperature. After stirring for 15 min, 2-phenylethanethiol (10 mmol, 1.4 g) was added, and the solution was stirred for 15 min 2 h. A cold aqueous solution (25 ml) containing NaBH₄ (20 mmol, 0.8 g) was then rapidly added to the solution, and the solution was then stirred at room temperature. After 15 h, the THF solvent was evaporated, and the remaining red brown powder was washed with methanol to remove excess thiol and other byproducts. The Au₂₅(SC₂H₄Ph)₁₈ clusters were extracted from the dried sample using acetonitrile.
19 General Procedure and the Analytical Data of some Typical Compounds The reaction of aniline (1a) with phenylacetylene (2a) was performed as follows. The prepared 1 mM Au₂₅(SC₂H₄Ph)₁₈nanocluster solution in toluene (0.5 mL) was added to a Schlenk flask and the solvent was evaporated. Then, 1a (0.5 mmol, 47 mg) and 2a (1.5 mmol, 153 mg) were added, and the solution was stirred for 24 h at 70 °C under O₂ (balloon). The chemical yield of imine 3a was determined by integrating the ¹H NMR spectrum with respect to an internal standard (1,3,5-trimethoxybenzene). Compound 3a was isolated by column chromatography (25 μm silica gel, n-hexane/ethyl acetate = 99:1). The yield was 63% (61 mg). 3a N-(1-Phenylethylidene)benzenamine Yellow solid; mp 40–41 °C. ¹H NMR (400 MHz CDCl₃): δ = 7.98–7.96 (2 H, m), 7.45–7.44 (3 H, m), 7.34 (2 H, t, J = 7.7 Hz), 7.08 (1 H, t, J = 7.2 Hz), 6.79 (2 H, d, J = 7.9 Hz), 2.22 (3 H, s); ¹³C NMR (100 MHz CDCl₃): δ = 165.48 (C), 151.65 (C), 139.42 (C), 130.46 (CH), 128.94 (CH), 128.36 (CH), 127.14 (CH), 123.20 (CH), 119.36 (CH), 17.38 (CH₃). GC-MS (EI): m/z (relative intensity) = 195 (53) [M]⁺, 180 (100), 118 (12). 3b N-(1-Phenylethylidene)-1-naphthalenamine Yellow solid; mp 85–86 °C. ¹H NMR (400 MHz CDCl₃) δ = 8.12–8.10 (2 H, m), 7.84–7.77 (2 H, m), 7.60–7.40 (7 H, m), 6.78 (1 H, d, J = 7.2 Hz), 2.19 (3 H, s). ¹³C NMR (400 MHz CDCl₃): δ = 166.42 (C), 147.93 (C), 139.20 (C), 134.15 (C), 130.64 (CH), 128.43 (CH), 127.94 (CH), 127.28 (CH), 126.08 (CH), 125.90 (C), 125.88 (CH), 125.37 (CH), 123.55 (CH), 123.21 (CH), 113.44 (CH), 17.66 (CH₃); GC-MS (EI) m/z (relative intensity) = 246 (12), 245 (62) [M]⁺, 231 (20), 230 (100), 128 (6), 127 (53).

20a Dharmaratne AC, Krick T, Dass A. J. Am. Chem. Soc. 2009; 131: 13604
20b Yamazoe S, Takano S, Kurashige W, Yokoyama T, Nitta K, Negishi Y, Tsukuda T. Nat. Commun. 2016; 7: 10414

Supplementary Material

Supporting Information