Efficient and Highly Enantioselective Aerobic Oxidation–Michael–Carbocyclization Cascade Transformations by Integrated Pd(0)-CPG Nanoparticle/Chiral Amine Relay Catalysis

Abstract

A series of highly diastereo- and enantioselective aerobic oxidation–Michael–carbocyclization cascade transformations by integrated heterogeneous Pd(0)-CPG nanoparticle/chiral amine relay catalysis are disclosed. The heterogeneous Pd(0)-CPG nanoparticle catalysts were efficient for both the sequential aerobic oxidation and dynamic kinetic asymmetric Michael–carbocyclization transformations, resulting in 1) oxidation of a variety of allylic alcohols to enals and 2) formation of cyclopentenes containing an all-carbon quaternary stereocenter in good to high yields with up to 20:1 dr and 99.5:0.5 er.

Key words

asymmetric cocatalysis - aerobic oxidations - relay catalysis - integrated heterogeneous catalysis - integrated homogeneous catalysis - quaternary stereocenters

• References

• 1 Corey EJ, Cheng X.-M. The Logic of Chemical Synthesis . Wiley-Interscience; New York: 1995
• 2a Mayer SF, Kroutil W, Faber K. Chem. Rev. 2006; 35: 332
• 2b Ricca E, Brucher B, Schrittwieser JH. Adv. Synth. Catal. 2011; 353: 2239
• 3a Tietze LF. Chem. Rev. 1996; 96: 115
• 3b Nicolaou KC, Edmonds DJ, Bulger PG. Angew. Chem. Int. Ed. 2006; 45: 7134
• 3c Guo H, Ma J. Angew. Chem. Int. Ed. 2006; 45: 354
• 3d Ramon DJ, Yus M. Angew. Chem. Int. Ed. 2005; 44: 1602
• 4a Veum L, Hanefeld U. Chem. Commun. 2006; 825
• 4b Sheldon RA, Arends I, Hanefeld U. Green Chemistry and Catalysis . Wiley-VCH; Weinheim: 2007
• 4c Lee JM, Na Y, Han H, Chang S. Chem. Soc. Rev. 2004; 33: 302
• 5a Shao Z, Zhang H. Chem. Soc. Rev. 2009; 38: 2745
• 5b Du Z, Shao Z. Chem. Soc. Rev. 2013; 42: 1337
• 5c Allen AE, MacMillan DW. C. Chem. Sci. 2012; 3: 633

For selected examples, see:
• 6a Ibrahem I, Córdova A. Angew. Chem. Int. Ed. 2006; 45: 1952
• 6b Silvero DL, Torker S, Pilyugina T, Vieira EM, Snapper ML, Haeffner F, Hoveyda AH. Nature 2013; 494: 216
• 6c Ibrahem I, Samec JS. M, Bäckvall J.-E, Córdova A. Tetrahedron Lett. 2005; 46: 3965
• 6d Sorimachi K, Terada M. J. Am. Chem. Soc. 2008; 130: 14452
• 6e Han Z.-Y, Xiao H, Chen X.-H, Gong L.-Z. J. Am. Chem. Soc. 2009; 131: 9182
• 6f Rueping M, Dufour J, Maji MS. Chem. Commun. 2012; 48: 3406
• 6g Yang T, Ferrali A, Campbell L, Dixon DJ. Chem. Commun. 2008; 2923
• 6h Binder JT, Crone B, Haug TT, Menz H, Kirsch SF. Org. Lett. 2008; 10: 1025
• 6i Jensen KL, Franke PT, Arróniz C, Kobbelgaard S, Jørgensen KA. Chem. Eur. J. 2010; 16: 1750
• 6j Yu C, Zhang Y, Zhang S, He J, Wang W. Tetrahedron Lett. 2010; 51: 1742
• 6k Vulovic B, Bihelovic F, Matovic R, Saicic RN. Tetrahedron 2009; 65: 10485
• 6l Mukherjee S, List B. J. Am. Chem. Soc. 2007; 129: 11336
• 6m Binder JT, Crone B, Haug TT, Menz H, Kirsch SF. Org. Lett. 2008; 10: 1025
• 6n Liu D, Xie F, Zhang W. Tetrahedron Lett. 2007; 48: 7591
• 6o Beeson TD, Mastracchio A, Hong J, Ashton K, MacMillan DW. C. Science 2007; 316: 582
• 6p Jiang G, List B. Angew. Chem. Int. Ed. 2011; 50: 9471
• 6q Cherevatskaya M, Füldner S, Harlander C, Neumann M, Kümmel S, Dankesreiter S, Pfitzner A, Zeitler K, König B. Angew. Chem. Int. Ed. 2012; 51: 4062
• 6r Lin S, Zhao G.-L, Deiana L, Sun J, Zhang Q, Leijonmarck H, Córdova A. Chem. Eur. J. 2010; 16: 13930
• 6s Sun W, Zhu G, Wu C, Hong L, Wang R. Chem. Eur. J. 2012; 18: 13959
• 7a Thomas JM. Design and Applications of Single-Site Heterogeneous Catalysts – Contributions to Green Chemistry, Clean Technology and Sustainability. Imperial College Press; London: 2012
• 7b Corma A, Garcia H. Top. Catal. 2008; 48: 8
• 7c van Heerbeek R, Kamer PC. J, van Leeuwen PW. N. M, Reek JN. H. Chem. Rev. 2002; 102: 3717
• 8a Anastas PT, Warner JC. Green Chemistry: Theory and Practice . Oxford University Press; Oxford: 2000
• 8b Baldini R. Eco-Friendly Synthesis of Fine Chemicals, RSC Green Chemistry Series. Royal Society of Chemistry; London: 2009
• 9 Deiana, L.; Jiang, Y.; Palo-Nieto, C.; Afewerki, S.; Incerti-Pradillos, C. A.; Verho, O.; Tai, C.-W.; Johnston, E.; Córdova, A. Angew. Chem. Int. Ed. 2014; DOI: 10.1002/anie.201310216.
• 10a Ping EW, Wallace R, Pierson J, Fuller TF, Jones CW. Micropor. Mesopor. Mater. 2010; 132: 174
• 10b Shakeri M, Tai C.-W, Göthelid E, Oscarsson S, Bäckvall JE. Chem. Eur. J. 2011; 17: 13269
• 10c Johnston EV, Verho O, Kärkäs MD, Shakeri M, Tai C.-W, Palmgren P, Eriksson K, Oscarsson S, Bäckvall J.-E. Chem. Eur. J. 2012; 18: 12202
• 10d Deiana L, Afewerki S, Palo-Nieto C, Verho O, Johnston EV, Córdova A. Sci. Rep. 2012; 2: 851
• 10e Long W, Brunelli NA, Didas SA, Ping EW, Jones CW. ACS Catal. 2013; 3: 1700
• 11a Ching LL, Erathodiyil N, Ying JY. Acc. Chem. Res. 2013; 8: 1825
• 11b Favier I, Madec D, Teuma E, Gomez M. Curr. Org. Chem. 2011; 15: 3127
• 11c Yin L, Liebscher J. Chem. Rev. 2007; 107: 133


• 12a Pon RT. Current Protocols in Nucleic Acid Chemistry . Beaucage SL, Glick GD, Bergström DE, Jones RA. Wiley; New York: 2000
• 12b Pon RT. Solid-Phase Supports for Oligonucleotide Synthesis. In Methods in Molecular Biology: Protocols for Oligonucleotides and Analogs. Vol. 20. Agarwal S. Humana Press; Totowa, NJ: 1993: 465-497


• 13a Tonks L, Anson MS, Hellgardt K, Mirza AR, Thompson DF, Williams JM. J. Tetrahedron Lett. 1997; 38: 4319

This technique has also been used for immobilization of Ru, see:
• 13b Wan KT, Davis ME. Nature 1994; 370: 449


• 14a Li J, Mau AW.-H, Strauss CR. Chem. Commun. 1997; 1275
• 14b Freitag J, Hermann M, Nuchter M, Ondruschka B, Schneider F, Stolle A. Optica Applicata 2005; 35: 745
• 14c Bonrath W, Ondruschka B, Schmoeger C, Stolle A. Int. Patent WO2010/020671 A1, 2008 ; Chem. Abstr. 2010, 152, 311257.
• 15a Afewerki S, Ibrahem I, Rydfjord J, Breistein P, Córdova A. Chem. Eur. J. 2012; 18: 2972
• 15b Ibrahem I, Breistein P, Córdova A. Angew. Chem. Int. Ed. 2011; 50: 12036
• 15c Ibrahem I, Ma G, Afewerki S, Córdova A. Angew. Chem. Int. Ed. 2013; 52: 878
• 15d Ma G, Afewerki S, Deiana L, Palo-Nieto C, Liu L, Sun J, Ibrahem I, Córdova A. Angew. Chem. Int. Ed. 2013; 52: 6050
• 15e Ibrahem I, Santoro S, Himo F, Córdova A. Adv. Synth. Catal. 2011; 353: 245
• 15f Santoro, S.; Deiana, L.; Zhao, G. -L. Lin, S.; Himo, F.; Córdova, A., manuscript in preparation.
• 16a Corey EJ. Angew. Chem. Int. Ed. 1998; 37: 388
• 16b Trost BM, Jiang C. Synthesis 2006; 369
• 16c Douglas CJ, Overman LE. Proc. Nat. Acad. Sci. U.S.A. 2004; 101: 5363
• 17 Zhao G.-L, Ullah F, Deiana L, Lin S, Zhang Q, Sun J, Ibrahem I, Dziedzic P, Córdova A. Chem. Eur. J. 2010; 16: 1585
• 18 For a review on the use of protected prolinols as catalysts, see: Mielgo A, Palomo C. Chem. Asian J. 2008; 3: 922