Bench-Stable and Recoverable Palladium(I) Dimer as an Efficient Catalyst for Heck Cross-Coupling

Theresa Sperger; Christopher K. Stirner; Franziska Schoenebeck

doi:10.1055/s-0036-1588318

Synthesis, Inhaltsverzeichnis

Synthesis 2017; 49(01): 115-120
DOI: 10.1055/s-0036-1588318

paper

Bench-Stable and Recoverable Palladium(I) Dimer as an Efficient Catalyst for Heck Cross-Coupling

Theresa Sperger

Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany eMail: franziska.schoenebeck@rwth-aachen.de

,

Christopher K. Stirner

Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany eMail: franziska.schoenebeck@rwth-aachen.de

,

Franziska Schoenebeck*

Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany eMail: franziska.schoenebeck@rwth-aachen.de

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

The application of air- and moisture-stable dinuclear palladium(I) complex [Pd(μ-I)(Pt-Bu₃)]₂ as an efficient catalyst for the Heck cross-coupling reaction of aryl iodides and bromides with acrylates and styrenes is described. The developed protocol is robust and operationally simple and shows a high functional-group tolerance. The employed palladium(I) dimer catalyst is highly robust under these nucleophilic as well as elevated-temperature conditions, allowing its recovery after reaction completion and recycling.

Key words

palladium(I) dimer - cross-coupling - Heck reaction - dinuclear catalysis - alkenes - catalyst recycling

Volltext

Referenzen

References

1a Heck RF, Nolley JP. J. Org. Chem. 1972; 37: 2320
1b de Meijere A, Diederich F. Metal-Catalyzed Cross-Coupling Reactions . Wiley-VCH; Weinheim: 2008. 2nd ed.

2a Johansson Seechurn CC. C, Kitching MO, Colacot TJ, Snieckus V. Angew. Chem. Int. Ed. 2012; 51: 5062
2b Colacot T. New Trends in Cross-Coupling: Theory and Applications . Royal Society of Chemistry; Cambridge: 2015
2c Whitcombe NJ, Hii KK, Gibson SE. Tetrahedron 2001; 57: 7449
2d Cabri W, Candiani I. Acc. Chem. Res. 1995; 28: 2
2e Felpin F.-X, Nassar-Hardy L, Le Callonnec F, Fouquet E. Tetrahedron 2011; 67: 2815
2f Beletskaya IP, Cheprakov AV. Chem. Rev. 2000; 100: 3009

3a Shaughnessy KH, Kim P, Hartwig JF. J. Am. Chem. Soc. 1999; 121: 2123
3b Littke AF, Fu GC. J. Org. Chem. 1999; 64: 10

4 Littke AF, Fu GC. J. Am. Chem. Soc. 2001; 123: 6989
5 Barnard C. Platin. Met. Rev. 2008; 52: 38
6 Yin L, Liebscher J. Chem. Rev. 2007; 107: 133

7a Organ MG, Chass GA, Fang D.-C, Hopkinson AC, Valente C. Synthesis 2008; 2776
7b Valente C, Çalimsiz S, Hoi KH, Mallik D, Sayah M, Organ MG. Angew. Chem. Int. Ed. 2012; 51: 3314
7c Kinzel T, Zhang Y, Buchwald SL. J. Am. Chem. Soc. 2010; 132: 14073
7d Marion N, Nolan SP. Acc. Chem. Res. 2008; 41: 1440

8a Stambuli JP, Kuwano R, Hartwig JF. Angew. Chem. Int. Ed. 2002; 41: 4746
8b Prashad M, Mak XY, Liu Y, Repic O. J. Org. Chem. 2003; 68: 1163
8c Hooper MW, Utsunomiya M, Hartwig JF. J. Org. Chem. 2003; 68: 2861
8d Christmann U, Vilar R. Angew. Chem. Int. Ed. 2005; 44: 366
8e Hama T, Culkin DA, Hartwig JF. J. Am. Chem. Soc. 2006; 128: 4976
8f Hill LL, Crowell JL, Tutwiler SL, Massie NL, Hines C, Griffin ST, Rogers RD, Shaughnessy KH, Grasa GA, Johansson Seechurn CC. C, Li H, Colacot TJ, Chou J, Woltermann CJ. J. Org. Chem. 2010; 75: 6477
8g Proutière F, Aufiero M, Schoenebeck F. J. Am. Chem. Soc. 2012; 134: 606
8h Mamone P, Grunberg MF, Fromm A, Khan BA, Gooßen LJ. Org. Lett. 2012; 14: 3716

9a Colacot T. Platin. Met. Rev. 2009; 53: 183
9b Pd(I)–iodo dimer 2 was first synthesized by: Vilar R, Mingos DM. P, Cardin CJ. J. Chem. Soc., Dalton Trans. 1996; 4313
9c An improved synthesis of the corresponding Pd(I)–bromo dimer 1 for commercial applications was developed by Colacot and co-workers (Patent): Colacot TJ, Hooper MW, Grasa GA. (Johnson Matthey) WO2011/12889A1, 2011

10a Bonney KJ, Proutière F, Schoenebeck F. Chem. Sci. 2013; 4: 4434
10b Kalvet I, Bonney KJ, Schoenebeck F. J. Org. Chem. 2014; 79: 12041

11a Yin G, Kalvet I, Schoenebeck F. Angew. Chem. Int. Ed. 2015; 54: 6809
11b Aufiero M, Sperger T, Tsang AS, Schoenebeck F. Angew. Chem. Int. Ed. 2015; 54: 10322

12 Aufiero M, Scattolin T, Proutière F, Schoenebeck F. Organometallics 2015; 34: 5191

Mayr’s scale is based on the addition of nucleophiles to carbocations and Michael acceptors; see:

13a Maji B, Stephenson DS, Mayr H. ChemCatChem 2012; 4: 993
13b Richter D, Mayr H. Angew. Chem. Int. Ed. 2009; 48: 1958
13c Kempf B, Hampel N, Ofial AR, Mayr H. Chem. Eur. J. 2003; 9: 2209

14 ³¹P NMR only shows the presence of the free phosphine ligand t-Bu₃P. This is most likely a result of fast conversion of the Pd(I)–bromo dimer to the monophosphine Pd(0)–Pt-Bu₃, an accumulation of which leads to decomposition to Pd black and free phosphine ligand. Please see ref. 12 for further information.

Zusatzmaterial

Supporting Information