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, 249-252
16e 14e
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, 1113-1116 Without CO, biaryl compounds are obtained. Sakakura, T.; Sodeyama, T.; Tokunaga, Y.; Tanaka, M. Chemistry Lett. 1987, 2211-2214
Mechanism of Diarylation
Dimerization of Esters Sakakura, T.; Sodeyma, T.; Tanaka, M. Chem. Lett. 1988, 683-684
Synthesis of methyl cinnamate from Benzene and methyl acrylate Sasaki, K.; Sakakura, T.; Tokunaga, Y.; Wada, K.; Tanaka, M. Chem. Lett. 1988, 685-688
B. Synthesis of Ketone from Aldehyde through C-H Bond Activation Hydroacylation
Hydroacylation was named by Schwartz. Schwartz, J.; Cannon, J. B. J. Am. Chem. Soc. 1974, 96, 4721-4723
Intramolecular Hydroacylation Lochow, C. F.; Miller, R. G. J. Am. Chem. Soc. 1976, 98, 1281-1283 Vora, K. P.; Lochow, C. F.; Miller R. G. J. Organomet. Chem. 1980, 192, 257-264 Intramolecular Hydroacylation
<Principle of Le Chatelie> Isnard, P.; Denise, B.; Sneeden, R. P. A. J. Organomet. Chem. 1982, 240, 285-288 Marder, T. B.; Roe, D. C.; Milstein, D. Organometallics 1988, 7, 1451-1453 <Principle of Le Chatelie> Kondo, T.; Tsuji, Y.; Watanabe, Y. Tetrahedron Lett. 1987, 28, 6229-6230 Kondo, T.; Akazome, M.; Tsuji, Y.; Watanabe, Y. J. Org. Chem. 1990, 55, 1286-1291
Suggs, J. W. J. Am. Chem. Soc. 1978, 100, 640-641 Lee, H.; Jun, C.-H. Bull. Korean Chem. Soc 1995, 16, 66
Suggs, J. W. J. Am. Chem. Soc. 1979, 101, 489
Annulation Reaction Larock, R. C.; Doty, M. J.; Cacchi, S. J. Org. Chem. 1993, 58, 4579-4583
Synthesis of Cyclopentanone Derivatives Sakai, K.; Ide, J.; Oda, O.; Nakamura, N. Tetrahedron Lett. 1972, 13, 1287-1290
Isolation of intermediate, cis-hydrido pent-4-enoyl rhodium(III) complexes Milstein, D. J. Chem. Soc., Chem. Comm. 1982, 1357-1358 Stereochemistry of intramolecular hydroacylation Campbell, Jr. R. E.; Lochow, C. F.; Vora, K. P.; Miller, R. G. J. Am. Chem. Soc. 1980, 102, 5824-5830
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, 1821-1830
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.
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
Regeneration of Wilkinson’c complex Geoffroy, G. L.; Denton, D. A.; Keeney, M. E.; Bucks, R. R. Inorg. Chem. 1976, 15, 2382
Use in natural product synthesis Occidentanol Lanosterol derivatives annulene
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
0.002% without NMP
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
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
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.
Beck, C. M.; Rathmill, S. E.; Park, Y. J.; Chen, J.; Crabtree, R. H. Organometalics 1999, 18, 5311 Retard the formation of byproducts