ion from a primary OH group of glyc-erol. 223,231 A similar mechanism was proposed manyyears ago for alcohol oxidation on Pt/C, involving asecond step, the transfer of a hydride ion to the Ptsurface (Scheme 11). 8,87,237 We consider it more feasible that the rate-deter-mining step is the cleavage of the C-H bond at theR-carbon atom. A similar mechanism is now generallyaccepted for Au electrodes (Scheme 12). 238 Despite thestructural differences between Au nanoparticles andan extended Au electrode surface, there are alsosimilarities, such as the critical role of aqueousalkaline medium and the absence of deactivation dueto decomposition products (CO and C x H y frag-ments). 239,240 An important question is the nature of active siteson Au nanoparticles. Electrooxidation of ethanol onAu nanoparticles supported on glassy carbon re-quired the partial coverage of Au surface by oxides. 241 Another analogy might be the model proposed for COoxidation. 219,242,243 According to this suggestion, theactive site consists of an ensemble of metallic Auatoms and a cationic Au

Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts

Large-scale applications of transition metal-catalyzed couplings for the synthesis of pharmaceuticals.

The legacy of Gilbert Newton Lewis (1875-1946) pervades the lexicon of chemical bonding and reactivity. The power of his concept of donor-acceptor bonding is evident in the eponymous foundations of electron-pair acceptors (Lewis acids) and donors (Lewis bases). Lewis recognized that acids are not restricted to those substances that contain hydrogen (Bronsted acids), and helped overthrow the "modern cult of the proton". His discovery ushered in the use of Lewis acids as reagents and catalysts for organic reactions. However, in recent years, the recognition that Lewis bases can also serve in this capacity has grown enormously. Most importantly, it has become increasingly apparent that the behavior of Lewis bases as agents for promoting chemical reactions is not merely as an electronic complement of the cognate Lewis acids: in fact Lewis bases are capable of enhancing both the electrophilic and nucleophilic character of molecules to which they are bound. This diversity of behavior leads to a remarkable versatility for the catalysis of reactions by Lewis bases.

Lewis Base Catalysis in Organic Synthesis

2.1.8. Michael Reaction 2245 2.1.9. Others 2247 2.2. Cyclization Reactions 2248 2.2.1. Carbon Diels−Alder Reactions 2248 2.2.2. Aza-Diels−Alder Reactions 2252 2.2.3. Other Hetero-Diels−Alder Reactions 2255 2.2.4. Ionic Diels−Alder Reaction 2256 2.2.5. 1,3-Dipolar Cycloadditions 2256 2.2.6. Other Cycloaddition Reactions 2258 2.2.7. Prins-type Cyclization 2259 2.3. Friedel−Crafts Acylation and Alkylation 2259 2.4. Baylis−Hillman Reaction 2263 2.5. Radical Addition 2264 2.6. Heterocycle Synthesis 2267 2.7. Diazocarbonyl Insertion 2270 3. C−X (X ) N, O, P, Etc.) Bond Formation 2271 3.1. Aromatic Nitration and Sulfonylation 2271 3.2. Michael Reaction 2272 3.3. Glycosylation 2273 3.4. Aziridination 2275 3.5. Diazocarbonyl Insertion 2276 3.6. Ring-Opening Reactions 2277 3.7. Other C−X Bond Formations 2280 4. Oxidation and Reduction 2280 4.1. Oxidation 2280 4.2. Reduction 2281 5. Rearrangement 2283 6. Protection and Deprotection 2285 6.1. Protection 2285 6.2. Deprotection 2288 7. Polymerization 2291 8. Miscellaneous Reactions 2291 9. Lanthanide(II) Triflates in Organic Synthesis 2295 10. Conclusion 2295 11. Acknowledgment 2295 12. References 2295

Rare-earth metal triflates in organic synthesis

From 2000 to mid-2010: a fruitful decade for the synthesis of pyrazoles.

Oxidative aromatization of 1,3,5-trisubstituted pyrazolines and Hantzsch 1,4-dihydropyridines by Pd/C in acetic acid.

Direct and practical synthesis of 2-arylbenzoxazoles promoted by activated carbon.

Enantioselective addition of diorganozincs to aldehydes catalyzed by β-amino alcohols

Synthesis of Versatile Chiral N,P Ligands Derived from Pyridine and Quinoline

The complexes formed between titanium tetraalkoxide and chiral Schiff's bases make excellent catalysts for enantioselective trimethylsilylcyanation of aldehydes to optically active cyanohydrins in high optical yield.

Masahiko Hayashi

Papers

Oxidative aromatization of 1,3,5-trisubstituted pyrazolines and Hantzsch 1,4-dihydropyridines by Pd/C in acetic acid.

Direct and practical synthesis of 2-arylbenzoxazoles promoted by activated carbon.

Enantioselective addition of diorganozincs to aldehydes catalyzed by β-amino alcohols

Synthesis of Versatile Chiral N,P Ligands Derived from Pyridine and Quinoline

Enantioselective trimethylsilylcyanation of some aldehydes by chiral titanium schiff's base complexes