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

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

3. 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

4. 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

5. PART 2. N-H Bond Insertions

6. 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,

7. PART 2. N-H Bond Insertions

8. PART 2. N-H Bond Insertions

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

10. 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,

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

12. 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,

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

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

15. PART 4. S-H Bond Insertions

16. 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 ,

17. PART 4. S-H Bond Insertions
Zhou, Q, -L. Chem. Sci ,

18. PART 4. Si-H Bond Insertions

19. PART 4. Si-H Bond Insertions

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

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

22. 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 .

23. 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.

24. Thanks for your attention!