Mechanistic Insights into Palladium Leaching in Novel Pd/C-Catalyzed 
Boron-Heck Reaction of Arylboronic Acid

Mahesh G. Dighe; Sachin L. Lonkar; Mariam S. Degani

doi:10.1055/s-0032-1318110

Synlett, Inhaltsverzeichnis

Synlett 2013; 24(3): 347-350
DOI: 10.1055/s-0032-1318110

letter

Mechanistic Insights into Palladium Leaching in Novel Pd/C-Catalyzed Boron-Heck Reaction of Arylboronic Acid

Autor*innen

Mahesh G. Dighe

Department of Pharmaceutical Sciences and Technology, Institute of Chemical Technology, Matunga (E), Mumbai 400019, India Fax: +91(22)33611020 eMail: ms.degani@ictmumbai.edu.in
Sachin L. Lonkar

Department of Pharmaceutical Sciences and Technology, Institute of Chemical Technology, Matunga (E), Mumbai 400019, India Fax: +91(22)33611020 eMail: ms.degani@ictmumbai.edu.in
Mariam S. Degani*

Department of Pharmaceutical Sciences and Technology, Institute of Chemical Technology, Matunga (E), Mumbai 400019, India Fax: +91(22)33611020 eMail: ms.degani@ictmumbai.edu.in

Abstract

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Abstract

For the first time, Pd/C has been used for the Boron-Heck reaction, and the detailed mechanistic aspects of the reaction have been proven experimentally by a leaching test as well as by cyclic voltammetry studies. The results indicate that palladium leaching as a Pd(II) species, by oxidative addition of the arylboronic acid, is responsible for the reaction.

Key words

heterogeneous catalysis - Pd/C - arylboronic acids - palladium leaching - Boron-Heck reaction

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Referenzen

References and Notes
1 Karimi B, Behzadnia H, Elhamifar D, Akhavan PF, Efsahani FK, Zamani A. Synthesis 2010; 1399

2a Parrish JP, Jung YC, Shin SI, Jung KW. J. Org. Chem. 2002; 67: 7127
2b Hirabayashi K, Ando J, Kawashima J, Nishihara Y, Mori A, Hiyama T. Bull. Chem. Soc. Jpn. 2000; 73: 1409
2c Inoue A, Shinokubo H, Oshima K. J. Am. Chem. Soc. 2003; 125: 1484
2d Asano R, Moritani I, Fujiwara Y, Teranishi S. Bull. Chem. Soc. Jpn. 1973; 46: 2910
2e Matoba K, Motofusa S, Cho CS, Ohe K, Uemura S. J. Organomet. Chem. 1999; 574: 3
2f Heck RF. J. Am. Chem. Soc. 1968; 90: 5531

3 Cho CS, Uemura S. J. Organomet. Chem. 1994; 465: 85
4 Yoo KS, Park CP, Yoon CH, Sakaguchi S, O’Neill J, Jung KW. Org. Lett. 2007; 9: 3933

5a Lingh J, Enquist P-A, Pilotti A, Nilsson P, Larhed M. J. Org. Chem. 2007; 72: 7957
5b Enquist P.-A, Lindh J, Nilsson P, Larhed M. Green. Chem. 2006; 8: 338
5c Andappan MM. S, Nilsson P, Larhed M. Chem. Commun. 2004; 218
5d Andappan MM. S, Nilsson P, von Schenck H, Larhed M. J. Org. Chem. 2004; 69: 5212
5e Odell LR, Lindh J, Gustafsson T, Larhed M. Eur. J. Org. Chem. 2010; 2270
5f Nordqvist A, Bjorkelid C, Andaloussi M, Jansson AM, Mowbray SL, Karlen A, Larhed M. J. Org. Chem. 2011; 76: 8986

6 Lautens M, Mancuso J, Grover H. Synthesis 2004; 2006
7 Farrington EJ, Barnard CF. J, Rowsell E, Brown JM. Adv. Synth. Catal. 2005; 347: 185
8 Gottumukkala AL, Teichert JF, Heijnen D, Eisink N, Dijk S, Ferrer C, Hoogenband A, Minnaard AJ. J. Org. Chem. 2011; 76: 3498
9 Hsu C-M, Li C-B, Sun C.-H. J. Chin. Chem. Soc. 2009; 56: 873
10 Delcamp JH, Brucks AP, White MC. J. Am. Chem. Soc. 2008; 130: 11270
11 Andappan MM. S, Nilsson P, Larhed M. Mol. Diversity 2003; 7: 97

12a Augustine RL, Leary ST. J. Mol. Catal. A: Chem. 1995; 95: 277
12b Le Bars J, Specht U, Bradley JS, Blackmond DG. Langmuir 1999; 15: 7621
12c Sanjaykumar SR, Mukri BD, Patil S, Madras G, Hegde MS. J. Chem. Sci. 2011; 123: 47

13a Pal M. Synlett 2009; 2896
13b Zhao F, Murakami K, Shirai M, Arai M. J. Catal. 2000; 194: 479
13c Schmidt AF, Mametova LV. Kinet. Catal. 1996; 37: 406
13d Reetz MT, Westermann E. Angew. Chem. 2000; 112: 170
13e Schimdt AF, Smirnov VV, Starikova OV, Elaev AV. Kinet. Catal. 2001; 42: 223
13f Sawama Y, Takubo M, Mori S, Monguchi Y, Sajiki H. Eur. J. Org. Chem. 2011; 3361

14a Dams M, Drijkoningen L, Pauwels B, Tendeloo GV, De Vos DE, Jacobs PA. J. Catal. 2002; 209: 225
14b Ambulgekar GV, Bhanage BM, Samant SD. Tetrahedron Lett. 2005; 46: 2483
14c Yu K, Sommer W, Weck M, Jones CW. J. Catal. 2004; 226: 101
14d Yu K, Sommer W, Richardson JM, Weck M, Jones CW. Adv. Synth. Catal. 2005; 347: 161

15 Yuan G, Keane MA. Appl. Catal. B: Environ. 2004; 52: 301
16 Carlini C, Di Girolamo M, Macinai A, Marchionna M, Noviello M, Galletti AM. R, Sbrana G. J. Mol. Catal. A: Chem. 2003; 204: 721
17 General Procedure for the Pd/C-Catalyzed Boron-Heck Reaction In a typical example, arylboronic acid (1.0 mmol), olefin (2.0 mmol), pyrrolidine (1.5 mmol), TBAB (0.5 mmol), and 5% Pd/C (Pd 0.6 mol%) were charged in NMP (10 mL), and the reaction was heated to 80 °C under an oxygen atmosphere for the desired time. After the completion of the reaction, it was allowed to cool to r.t., and the palladium was filtered off for catalyst recovery. The filtrate was poured into H₂O (50 mL), and the crude product was extracted with hexane or Et₂O (3 × 5 mL). The combined organic layers were dried over Na₂SO₄, filtered, and concentrated under reduced pressure to give the crude product which was further purified by column chromatography.
18 Widegren JA, Finke RG. J. Mol. Catal. A: Chem. 2003; 198: 317
19 Biffis A, Zecca M, Basato M. Eur. J. Inorg. Chem. 2001; 1131
20 Conlon DA, Pipik B, Ferdinand S, Leblond CR, Sowa JR. Jr, Izzo B, Collin P, Ho G.-J, Williams JM, Shi Y.-J, Sun Y. Adv. Synth. Catal. 2003; 345: 931
21 Sekar N, Phatangare KR, Patil AB, Patil VS, Padalkar VS, Gupta VD, Umape PG. Curr. Chem. Lett. 2012; 1: 47

22a Jung YC, Mishra R, Yoon CH, Jung KW. Org. Lett. 2003; 5: 2231
22b Yoo KS, Yoon CH, Jung KW. J. Am. Chem. Soc. 2006; 128: 16384
22c Yoo KS, O’Neill J, Sakaguchi S, Giles R, Lee JH, Jung KW. J. Org. Chem. 2010; 75: 95

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