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Development of Chiral Spiro Phosphoramidites for Rhodium-Catalyzed Enantioselective Reactions |
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| Authors: | Dr Zhiyao Zheng Yuxi Cao Prof Dongsheng Zhu Dr Zheng Wang Prof Kuiling Ding |
| Institution: | 1. State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032 P. R. China
These authors contributed equally to this work.;2. Department of Chemistry, Northeast Normal University, Changchun, 130024 P. R. China State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032 P. R. China These authors contributed equally to this work.;3. Department of Chemistry, Northeast Normal University, Changchun, 130024 P. R. China;4. State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032 P. R. China |
| Abstract: | A series of 1,1′-spirobiindane-7,7′-diol ( SPINOL ) analogues bearing a 2,2′-dimethyl-, cyclopentyl-, or cyclohexyl-fused ring were synthesized, and their distinct structural features were elucidated by X-ray crystallography. On the basis of these scaffolds, chiral monophosphoramidite ligands 6 a – m were synthesized, which demonstrated excellent enantioselectivity in RhI-catalyzed asymmetric hydrogenation of a dehydro amino acid methyl ester. Ligands 6 a – m were also successfully applied in the RhI-catalyzed enantioselective 4+2] cycloaddition of α,β-unsaturated imines with isocyanates, which afforded the corresponding pyrimidinones in good yields (60–92 %) with high enantioselectivities (75–92 % ee). |
| Keywords: | asymmetric catalysis cycloaddition ligand design rhodium spiro compounds |