ion. The oxidative addition mechanism was originally proposed22i because of the lack of a strong rate dependence on polar factors and on the acidity of the medium. Later, however, the electrophilic substitution mechanism also was proposed. Recently, the oxidative addition mechanism was confirmed by investigations into the decomposition and protonolysis of alkylplatinum complexes, which are the reverse of alkane activation. There are two routes which operate in the decomposition of the dimethylplatinum(IV) complex Cs2Pt(CH3)2Cl4. The first route leads to chloride-induced reductive elimination and produces methyl chloride and methane. The second route leads to the formation of ethane. There is strong kinetic evidence that the ethane is produced by the decomposition of an ethylhydridoplatinum(IV) complex formed from the initial dimethylplatinum(IV) complex. In D2O-DCl, the ethane which is formed contains several D atoms and has practically the same multiple exchange parameter and distribution as does an ethane which has undergone platinum(II)-catalyzed H-D exchange with D2O. Moreover, ethyl chloride is formed competitively with H-D exchange in the presence of platinum(IV). From the principle of microscopic reversibility it follows that the same ethylhydridoplatinum(IV) complex is the intermediate in the reaction of ethane with platinum(II). Important results were obtained by Labinger and Bercaw62c in the investigation of the protonolysis mechanism of several alkylplatinum(II) complexes at low temperatures. These reactions are important because they could model the microscopic reverse of C-H activation by platinum(II) complexes. Alkylhydridoplatinum(IV) complexes were observed as intermediates in certain cases, such as when the complex (tmeda)Pt(CH2Ph)Cl or (tmeda)PtMe2 (tmeda ) N,N,N′,N′-tetramethylenediamine) was treated with HCl in CD2Cl2 or CD3OD, respectively. In some cases H-D exchange took place between the methyl groups on platinum and the, CD3OD prior to methane loss. On the basis of the kinetic results, a common mechanism was proposed to operate in all the reactions: (1) protonation of Pt(II) to generate an alkylhydridoplatinum(IV) intermediate, (2) dissociation of solvent or chloride to generate a cationic, fivecoordinate platinum(IV) species, (3) reductive C-H bond formation, producing a platinum(II) alkane σ-complex, and (4) loss of the alkane either through an associative or dissociative substitution pathway. These results implicate the presence of both alkane σ-complexes and alkylhydridoplatinum(IV) complexes as intermediates in the Pt(II)-induced C-H activation reactions. Thus, the first step in the alkane activation reaction is formation of a σ-complex with the alkane, which then undergoes oxidative addition to produce an alkylhydrido complex. Reversible interconversion of these intermediates, together with reversible deprotonation of the alkylhydridoplatinum(IV) complexes, leads to multiple H-D exchange

Activation of c-h bonds by metal complexes

Graphite oxide is one of the main precursors of graphene-based materials, which are highly promising for various technological applications because of their unusual electronic properties Although epoxy and hydroxyl groups are widely accepted as its main functionalities, the complete structure of graphite oxide has remained elusive By interpreting spectroscopic data in the context of the major functional groups believed to be present in graphite oxide, we now show evidence for the presence of five- and six-membered-ring lactols On the basis of this chemical composition, we devised a complete reduction process through chemical conversion by sodium borohydride and sulfuric acid treatment, followed by thermal annealing Only small amounts of impurities are present in the final product (less than 05 wt% of sulfur and nitrogen, compared with about 3 wt% with other chemical reductions) This method is particularly effective in the restoration of the π-conjugated structure, and leads to highly soluble and conductive graphene materials

New insights into the structure and reduction of graphite oxide

4.2.8. Reductive Coupling 3109 5. Reaction of Aromatic Compounds 3110 5.1. Electrophilic Substitutions 3110 5.2. Radical Substitution 3111 5.3. Oxidative Coupling 3111 5.4. Photochemical Reactions 3111 6. Reaction of Carbonyl Compounds 3111 6.1. Nucleophilic Additions 3111 6.1.1. Allylation 3111 6.1.2. Propargylation 3120 6.1.3. Benzylation 3121 6.1.4. Arylation/Vinylation 3121 6.1.5. Alkynylation 3121 6.1.6. Alkylation 3121 6.1.7. Reformatsky-Type Reaction 3122 6.1.8. Direct Aldol Reaction 3122 6.1.9. Mukaiyama Aldol Reaction 3124 6.1.10. Hydrogen Cyanide Addition 3125 6.2. Pinacol Coupling 3126 6.3. Wittig Reactions 3126 7. Reaction of R,â-Unsaturated Carbonyl Compounds 3127

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update

Over the past decade, the most significant, conceptual advances in the field of fluorination were enabled most prominently by organo- and transition-metal catalysis. The most challenging transformation remains the formation of the parent C-F bond, primarily as a consequence of the high hydration energy of fluoride, strong metal-fluorine bonds, and highly polarized bonds to fluorine. Most fluorination reactions still lack generality, predictability, and cost-efficiency. Despite all current limitations, modern fluorination methods have made fluorinated molecules more readily available than ever before and have begun to have an impact on research areas that do not require large amounts of material, such as drug discovery and positron emission tomography. This Review gives a brief summary of conventional fluorination reactions, including those reactions that introduce fluorinated functional groups, and focuses on modern developments in the field.

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Introduction of Fluorine and Fluorine-Containing Functional Groups

Direct C-H transformation via iron catalysis.

Synopsis: With the addition of titanium tetrachloride, silyl enol ethers can react with either aldehydes or ketones forming crossed aldol products. The carbonyl group of the aldehyde or ketone is activated by titanium tetrachloride, allowing for nucleophilic attack by a silyl enol ether at the carbonyl carbon (a titanium chelate forms as an intermediate). This addition reaction is dependent upon the metal salt, solvent, and temperature used. Critique: The fact that various reaction conditions were studied to find optimal reaction conditions that gave the highest yield of cross-aldol addition products strengthened the findings in this paper. Mukaiyama and coworkers concluded first that titanium chloride was best for this reaction compared to boron trifluoride etherate and stannic chloride. Secondly, it was observed that methylene chloride gave cross-aldol products in good yield while no reaction was observed in both diethyl ether and THF. Finally, reaction with aldehydes is favored at -78 o C while ketone reaction is favored at room temperature. It was also interesting to see that the use of unsymmetric ketones allows for regiospecific addition reactions at the olefinic position on the silyl enol ether.

New cross-aldol reactions. Reactions of silyl enol ethers with carbonyl compounds activated by titanium tetrachloride

Recent advances in the aerobic oxygenations of olefins using transition-metal complex catalysts are reviewed. The main topics focused on are the cobalt(II)-complex-catalyzed oxygenation of olefins, nickel(II)-complex-catalyzed aerobic epoxidation, enantioselective, aerobic epoxidation using chiral manganese(III) complex catalysts, aerobic Baeyer–Villiger oxidation and direct oxygenation of aromatic compounds.

Recent Advances in Aerobic Oxygenation

In the presence of a chiral promoter consisting of tin(II) triflate, a chiral diamine, and tributylin fluoride, the silyl enol ether of S-ethyl ethanethioate or S-tert-butyl ethanetioate reacts with aldehydes to afford the corresponding aldol-type adducts in good yields with high enantioselectivities. In the reaction of silyl enol ether of S-ethyl propanethioate with aldehydes, perfect stereochemical control is attained by the combined use of tin(II) triflate, a chiral diamine, and dibutylin diacetate. A wide variety of aldehydes, including aliphatic, α,β-unsaturated, and aromatic aldehydes, are applicable to this reaction. The chiral promoters are characterized by 119 Sn NMR spectra and proved to form the three-component complexes, which behave as chiral Lewis acids. The reaction proceeds directly from silyl enol ethers without any accompanying metal exchange on the enolates

Asymmetric aldol reaction between achiral silyl enol ethers and achiral aldehydes by use of a chiral promoter system

This Review describes the basic concepts that have guided our exploration of new chemical reactions by giving examples of results from my research group. Our strategy of carrying out research is to investigate three to four different topics at a time so we can gather as many results as possible. These may at first appear unrelated to each other but may have the potential to be united into a greater hypothesis after repeated feedback. Three scenarios from our research are presented: the "oxidative-reductive condensation reaction" devised in 1960, which after an interval of nearly 40 years brought forth the new concept of using compounds of structure Ph(2)POR as reducing reagents; the "TiCl(4)-aldol reaction" of 1973 that eventually led to the present "base-promoted aldol reaction" through a chain of ideas; and the "glycosylation reaction using fluorosugars" from 1984 which recently bloomed into "stereocontrolled glycosylation". Thus, it can be said that by reviewing what we had done before, we were able to expand on it to achieve new outcomes.

Teruaki Mukaiyama

Papers

New cross-aldol reactions. Reactions of silyl enol ethers with carbonyl compounds activated by titanium tetrachloride

New cross-aldol reactions. Reactions of silyl enol ethers with carbonyl compounds activated by titanium tetrachloride

Recent Advances in Aerobic Oxygenation

Asymmetric aldol reaction between achiral silyl enol ethers and achiral aldehydes by use of a chiral promoter system

Explorations into new reaction chemistry.