A new class of versatile chiral-bridged atropisomeric diphosphine ligands: remarkably efficient ligand syntheses and their applications in highly enantioselective hydrogenation reactions

Journal of the American Chemical Society
Liqin QiuAlbert S C Chan

Abstract

A series of chiral diphosphine ligands denoted as PQ-Phos was prepared by atropdiastereoselective Ullmann coupling and ring-closure reactions. The Ullmann coupling reaction of the biaryl diphosphine dioxides is featured by highly efficient central-to-axial chirality transfer with diastereomeric excess >99%. This substrate-directed diastereomeric biaryl coupling reaction is unprecedented for the preparation of chiral diphosphine dioxides, and our method precludes the tedious resolution procedures usually required for preparing enantiomerically pure diphosphine ligands. The effect of chiral recognition was also revealed in a relevant asymmetric ring-closure reaction. The chiral tether bridging the two aryl units creates a conformationally rigid scaffold essential for enantiofacial differentiation; fine-tuning of the ligand scaffold (e.g., dihedral angles) can be achieved by varying the chain length of the chiral tether. The enantiomerically pure Ru- and Ir-PQ-Phos complexes have been prepared and applied to the catalytic enantioselective hydrogenations of alpha- and beta-ketoesters (C=O bond reduction), 2-(6'-methoxy-2'-naphthyl)propenoic acid, alkyl-substituted beta-dehydroamino acids (C=C bond reduction), and N-heteroaromatic c...Continue Reading

References

Mar 15, 2003·The Journal of Organic Chemistry·Jing WuAlbert S C Chan
Aug 9, 2003·Journal of the American Chemical Society·Wenjun TangXumu Zhang
Aug 28, 2003·Journal of the American Chemical Society·Wen-Bo WangYong-Gui Zhou
Jan 6, 2004·Angewandte Chemie·Séverine JeulinPhilippe Dellis
Mar 20, 2004·Proceedings of the National Academy of Sciences of the United States of America·Séverine JeulinPhilippe Dellis
Apr 7, 2004·Proceedings of the National Academy of Sciences of the United States of America·Liqin QiuAlbert S C Chan
Feb 25, 2005·Proceedings of the National Academy of Sciences of the United States of America·Jing WuAlbert S C Chan
Feb 26, 2005·The Journal of Organic Chemistry·Neil W BoazJames A Ponasik
Apr 14, 2005·Chemistry : a European Journal·Fuk Yee KwongAlbert S C Chan
Jan 5, 2001·Angewandte Chemie·Manabu HatanoKoichi Mikami

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Citations

Aug 13, 2011·Chemical Reviews·Vellaisamy SridharanJ Carlos Menéndez
Oct 19, 2007·Proceedings of the National Academy of Sciences of the United States of America·Liqin QiuAlbert S C Chan
Dec 15, 2015·Organic Letters·Zhenhua Zhang, Haifeng Du
Aug 22, 2015·Journal of the American Chemical Society·Feng ChenMatthias Beller
Apr 24, 2015·Chemical Society Reviews·J Wencel-DelordF Colobert
Feb 21, 2014·Angewandte Chemie·Jędrzej WysockiFrank Glorius
Aug 24, 2012·Chemistry : a European Journal·Takuto NaganoKazushi Mashima
Jul 27, 2007·Angewandte Chemie·Rainer Kramer, Reinhard Brückner
Apr 12, 2008·Angewandte Chemie·Christopher M ByrneGeoffrey W Coates
Feb 9, 2010·Chemistry : a European Journal·Magnus RuepingFenja R Schoepke
Apr 27, 2010·Chemical Society Reviews·Barbara WeinerBen L Feringa
Jun 10, 2010·Organic & Biomolecular Chemistry·Weijun TangAlbert S C Chan
Feb 10, 2012·Chemical Society Reviews·David J AgerJohannes G de Vries
Jun 27, 2012·Organic & Biomolecular Chemistry·Hajar el HajjoujiFernando López Ortiz
Apr 23, 2013·Chemistry : a European Journal·Agnieszka BartoszewiczBelén Martín-Matute
Mar 7, 2013·Chemistry : a European Journal·Steffen FleischerMatthias Beller
Apr 18, 2019·Beilstein Journal of Organic Chemistry·Hong YanHai-Chao Xu
Feb 9, 2012·Angewandte Chemie·Nuria OrtegaFrank Glorius
Nov 2, 2014·Angewandte Chemie·Zachary S KeanStephen L Craig

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