Asymmetric catalysis with substitutionally labile yet stereochemically stable chiral-at-metal iridium(III) complex.

作者: Haohua Huo , Chen Fu , Klaus Harms , Eric Meggers

DOI: 10.1021/JA4132505

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摘要: A metal-coordination-based high performance asymmetric catalyst utilizing metal centrochirality as the sole element of chirality is reported. The introduced substitutionally labile chiral-at-metal octahedral iridium(III) complex exclusively bears achiral ligands and effectively catalyzes enantioselective Friedel–Crafts addition indoles to α,β-unsaturated 2-acyl imidazoles (19 examples) with yields (75%–99%) enantioselectivities (90–98% ee) at low loadings (0.25–2 mol %). Counterintuitively, despite its substitutional lability, which mechanistically required for coordination imidazole substrate, metal-centered maintained throughout catalysis. This novel class reactive complexes will likely be value a large variety transformations.

参考文章(43)
Olivier Hamelin, Mickael Rimboud, Jacques Pécaut, Marc Fontecave, Chiral-at-metal ruthenium complex as a metalloligand for asymmetric catalysis. Inorganic Chemistry. ,vol. 46, pp. 5354- 5360 ,(2007) , 10.1021/IC7005502
Liangru Yang, Alex von Zelewsky, Huong P. Nguyen, Gilles Muller, Gaël Labat, Helen Stoeckli-Evans, Stereoselective synthesis of cyclometalated iridium(III) complexes: Characterization and photophysical properties Inorganica Chimica Acta. ,vol. 362, pp. 3853- 3856 ,(2009) , 10.1016/J.ICA.2008.10.011
Oleg Chepelin, Jakub Ujma, Xiaohua Wu, Alexandra M. Z. Slawin, Mateusz B. Pitak, Simon J. Coles, Julien Michel, Anita C. Jones, Perdita E. Barran, Paul J. Lusby, Luminescent, Enantiopure, Phenylatopyridine Iridium-Based Coordination Capsules Journal of the American Chemical Society. ,vol. 134, pp. 19334- 19337 ,(2012) , 10.1021/JA309031H
Gebhard Haberhauer, Thomas Oeser, Frank Rominger, A widely applicable concept for predictable induction of preferred configuration in C3-symmetric systems. Chemical Communications. pp. 2799- 2801 ,(2005) , 10.1039/B502158H
Christian Ganter, The chemistry of chiral heterometallocenes Journal of The Chemical Society-dalton Transactions. pp. 3541- 3548 ,(2001) , 10.1039/B108375A
Vinit Kumar, Tamaki Endoh, Kentaro Murakami, Naoki Sugimoto, Dehydration from conserved stem regions is fundamental for ligand-dependent conformational transition of the adenine-specific riboswitch Chemical Communications. ,vol. 48, pp. 9693- 9686 ,(2012) , 10.1039/C2CC34506D
Edwin C. Constable, Stereogenic metal centres – from Werner to supramolecular chemistry Chemical Society Reviews. ,vol. 42, pp. 1637- 1651 ,(2013) , 10.1039/C2CS35270B
SHUNSAKU OHTA, SATOSHI HAYAKAWA, KAZUKO NISHIMURA, MASAO OKAMOTO, Synthesis and application of imidazole derivatives: synthesis of (1-methyl-1H-imidazol-2-yl)methanol derivatives and conversion into carbonyl compounds Chemical & Pharmaceutical Bulletin. ,vol. 35, pp. 1058- 1069 ,(1987) , 10.1248/CPB.35.1058
Jeanne Crassous, Transfer of chirality from ligands to metal centers: recent examples Chemical Communications. ,vol. 48, pp. 9687- 9695 ,(2012) , 10.1039/C2CC31542D