Organic carbonylation, effect

CO into a metal-hydrogen bond, apparently analogous to the common insertion of CO into a metal-alkyl bond (6). Step (c) is the reductive elimination of an acyl group and a hydride, observed in catalytic decarbonylation of aldehydes (7,8). Steps (d-f) correspond to catalytic hydrogenation of an organic carbonyl compound to an alcohol that can be achieved by several mononuclear complexes (9JO). Schemes similar to this one have been proposed for the mechanism of CO reduction by heterogeneous catalysts, the latter considered to consist of effectively separate, one-metal atom centers (11,12). As noted earlier, however, this may not be a reasonable model. 

Organic superbases effectively generate carbonyl-stabilized ylides to promote Wittig reactions. In the synthesis of (-)-mycalolide A (68) by Panek and Liu, construction of... 

In 1999, we occasionally found that substituted 1,4-dUithio-1,3-butadienes (Fig. 1, di-lithio reagents for short) exhibit different reactivity patterns compared with their mono-lithium analogs toward organic carbonyl compounds [12-14]. We gradually recognized that the cooperative effect between the two C-Li moieties and the butadienyl bridge is essential for realizing such reaction patterns. 

Fluorinated Acids. This class of compounds is characterized by the strength of the fluorocarbon acids, eg, CF COOH, approaching that of mineral acids. This property results from the strong inductive effect of fluorine and is markedly less when the fluorocarbon group is moved away from the carbonyl group. Generally, their reactions are similar to organic acids and they find apphcations, particularly trifluoroacetic acid [76-05-1] and its anhydride [407-25-0] as promotors in the preparation of esters and ketones and in nitration reactions. 

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