1. Catalytic C-H Bond Activation to Organic Synthesis
A. Carbonylation
B. Hydroacylation
C. Dehydrogention
D. Orthoalkylation
A. Carbonylation through C-H Bond Activation
Sakakura, T; Tanaka, M. Chem. Lett. 1987,

2. 16e
14e

3. Cf. Orientation of Electrophilic Substitution Reaction in Aromatic Ring
(Friedel-Craft Acylation Reaction, Vilsemeyer Formylation, etc.)
Meta-directing
Sakakura, T.; Tanaka, M. Chemistry Lett. 1987,
Without CO, biaryl compounds are obtained.
Sakakura, T.; Sodeyama, T.; Tokunaga, Y.; Tanaka, M.
Chemistry Lett. 1987,

4. Mechanism of Diarylation

5. Dimerization of Esters
Sakakura, T.; Sodeyma, T.; Tanaka, M. Chem. Lett. 1988,

6. Synthesis of methyl cinnamate from Benzene and methyl acrylate
Sasaki, K.; Sakakura, T.; Tokunaga, Y.; Wada, K.; Tanaka, M.
Chem. Lett. 1988,

8. B. Synthesis of Ketone from Aldehyde
through C-H Bond Activation
Hydroacylation

9. Hydroacylation was named by Schwartz.
Schwartz, J.; Cannon, J. B. J. Am. Chem. Soc. 1974, 96,

10. Intramolecular Hydroacylation
Lochow, C. F.; Miller, R. G. J. Am. Chem. Soc. 1976, 98,
Vora, K. P.; Lochow, C. F.; Miller R. G. J. Organomet. Chem. 1980, 192,
Intramolecular Hydroacylation

11. <Principle of Le Chatelie>
Isnard, P.; Denise, B.; Sneeden, R. P. A. J. Organomet. Chem. 1982, 240,
Marder, T. B.; Roe, D. C.; Milstein, D. Organometallics 1988, 7,
<Principle of Le Chatelie>
Kondo, T.; Tsuji, Y.; Watanabe, Y. Tetrahedron Lett. 1987, 28,
Kondo, T.; Akazome, M.; Tsuji, Y.; Watanabe, Y. J. Org. Chem. 1990, 55,

12. Suggs, J. W. J. Am. Chem. Soc. 1978, 100,
Lee, H.; Jun, C.-H. Bull. Korean Chem. Soc 1995, 16, 66

13. Suggs, J. W. J. Am. Chem. Soc. 1979, 101, 489

14. Annulation Reaction
Larock, R. C.; Doty, M. J.; Cacchi, S. J. Org. Chem. 1993, 58,

15. Synthesis of Cyclopentanone Derivatives
Sakai, K.; Ide, J.; Oda, O.; Nakamura, N. Tetrahedron Lett. 1972, 13,

16. Isolation of intermediate,
cis-hydrido pent-4-enoyl rhodium(III) complexes
Milstein, D. J. Chem. Soc., Chem. Comm. 1982,
Stereochemistry of intramolecular hydroacylation
Campbell, Jr. R. E.; Lochow, C. F.; Vora, K. P.; Miller, R. G.
J. Am. Chem. Soc. 1980, 102,

17. Barnhart, R. W. ; Wang, X. ; Noheda, P. ; Bergens, S. H. ; Whelan, J
Barnhart, R. W.; Wang, X.; Noheda, P.; Bergens, S. H.; Whelan, J.; Bosnich, B.
J. Am. Chem. Soc. 1994, 116,

18. C. Decarbonylation through C-H Bond Activation
Common method for decarbonylation of aldehyde: oxidation of aldehyde
and pyrolysis of decarboxylation of the resulting carboxylic acid.
Some carboxylic acid is too stable to be decarboyxylated.

19. only product
Tsuji, J.; Ohno, K. A. J. Am. Chem. Soc. 1968, 90, 94
stoichiometric reaction
catalytic reaction
Ohno, K.; Tsuji, J. J. Am. Chem. Soc. 1968, 90, 99

20. Regeneration of Wilkinson’c complex
Geoffroy, G. L.; Denton, D. A.; Keeney, M. E.; Bucks, R. R.
Inorg. Chem. 1976, 15, 2382

21. Use in natural product synthesis
Occidentanol
Lanosterol derivatives
annulene

22. Retension of stereochemistry of carbon next to aldehyde
Walborsky, H. M.; Allen, L. E. J. Am. Chem. Soc. 1971, 93, 5465.
Trost, B. M.; Preckel, M. J. Am. Chem. Soc. 1973, 95, 7862.
Andrews, M. A.; Klaeren, S. A.; J. Chem. Soc., Chem. Comm. 1988, 1266. 
Andrews, M. A.; Gould, G. L.; Klaeren, S. A. J. Org. Chem. 1989, 54, 5257

23. 0.002% without NMP

24. Since the bond of common Rh and CO bond is very strong, it is hard to
Liberate CO. But CO binded to Rh+ species are easily to be dissociated
Due to weak p-back donation.
Doughty, D. H.; Pignolet, L. H.  J. Am. Chem. Soc. 1978, 100, 7083

25. Elimination of carboxylic ester
Meyer, M. D.; Kruse, L. I. J. Org. Chem. 1984, 49, 3195
Elimination of aldehyde under very mild conditions
isocyanate
O'connor, J. M.; Ma, J. J. Org. Chem. 1992, 57, 5075

27. Kondo, T.; Tantayanon, S.; Tsuji, Y.; Watanabe, Y. 
Tetrahedron Lett. 1989, 30, 4137
(CH3)3NO is a promoter to make unsaturation of Ru3(CO)12.

28. Beck, C. M.; Rathmill, S. E.; Park, Y. J.; Chen, J.; Crabtree, R. H.
Organometalics 1999, 18, 5311
Retard the formation of byproducts