Transition-Metal-Catalyzed Enantioselective Insertion of carbenes or carbenoids into the Heteroatom-Hydrogen Bond Reactions Xiaolei Lian 2014-04-26.

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Presentation transcript:

Transition-Metal-Catalyzed Enantioselective Insertion of carbenes or carbenoids into the Heteroatom-Hydrogen Bond Reactions Xiaolei Lian 2014-04-26

PART 1. Background The history of transition-metal-catalyzed X-H insertion

PART 1. Background The mechanism of transition-metal-catalyzed X-H insertion a ) a generally accepted insertion mechanism b) two distinct pathways in X-H insertion

Contents 1 2 3 4 5 N-H bond insertion O-H bond insertion S-H bond insertion 3 Si-H bond insertion 4 B-H bond insertion 5

PART 2. N-H Bond Insertions

PART 2. N-H Bond Insertions Entry Cu source Ligand Additive Time(h) Yield(%) ee(%) 1 Cu(MeCN)4PF6 (Sa, S, S)-1a none 2 78 43 CuOTf 83 5 3 CuCl 24 15 rac 4 NaBARF 94 98 Zhou, Q. –L. J. Am. Chem. Soc. 2007, 129, 5834-5835

PART 2. N-H Bond Insertions

PART 2. N-H Bond Insertions

PART 3. O-H Bond Insertions Intermolecular O-H Bond Insertions Fu, G. C. J. Am. Chem. Soc. 2006, 128, 4594-4595

PART 3. O-H Bond Insertions Intermolecular O-H Bond Insertions entry M source ligand time (h) yield(%) ee(%) 1 FeCl2.4H2O (Sa, S, S)-1a 15 87 86 2 (Sa, S, S)-1b 24 88 3 (Sa, S, S)-1c 93 98 4 (Sa, S, S)-1d 30 63 50 5 CuCl 90 80 6 CoCl2 48 23 82 7 NiCl2 81 8 AuCl - 9 AgOTf 42 10 [RhCl(CO)2]2 27 11 [RuCl2C6H6]2 45 67 Zhou, Q, -L. Nat. Chem. 2010, 2, 546-551

PART 3. O-H Bond Insertions Intermolecular O-H Bond Insertions

PART 3. O-H Bond Insertions Intermolecular O-H Bond Insertions First, the active transition metal are generally sensitive to water. Second, the small molecular structure of water makes chiral discrimination quite difficult. Fu, G. C. J. Am. Chem. Soc. 2006, 128, 4594-4595

PART 3. O-H Bond Insertions Intermolecular O-H Bond Insertions Zhou, Q, -L. Nat. Chem. 2010, 2, 546-551 Zhou, Q, -L. Angew. Chem. Int. Ed. 2008, 47, 932-934

PART 3. O-H Bond Insertions Intramolecular O-H Bond Insertions Zhou, Q, -L. J. Am. Chem. Soc. 2010, 132, 16374-16376 Zhou, Q, -L. Angew. Chem. Int. Ed. 2013, 52, 2555-2558

PART 4. S-H Bond Insertions

PART 4. S-H Bond Insertions First, the high coordination ability of S atom to the transition metal may destroy the active chiral catalyst. Second, the relative high stability of S ylide may facilitate the degeneration of metal-associated ylide to free yield, which lower the efficiency of chiral induction of catalyst. Zhou, Q, -L. Chem. Commun. 2009, 5362-5364

PART 4. S-H Bond Insertions Zhou, Q, -L. Chem. Sci. 2014, 1442-1448

PART 4. Si-H Bond Insertions

PART 4. Si-H Bond Insertions

PART 4. Si-H Bond Insertions Zhou, Q, -L. Angew. Chem. Int. Ed. 2008, 47, 8496-8498

PART 5. B-H Bond Insertions Zhou, Q, -L. J. Am. Chem. Soc. 2013, 132, 14094-14097

PART 5. Conclusion Remarks By use of copper or iron complex with chiral spiro-bisoxazoline ligands or –diimine ligands , the X-H insertions of diazo compounds have been accomplished with high excellent enantioselectivities .

PART 5. Conclusion Remarks For S whose ylide intermediate has high stability or α-Dizaoketone which trend to form free ylide intermediate II , the combination of 【M】with spiro phosphoric acid can achieve high enantioselective result.

Thanks for your attention!