Boronic Acids.pdf

Boronic Acids Boronic acids and their derivatives are among the most useful classes of organoboron molecules. Unlike many organometallic derivatives and most organoboranes, boronic acids are usually stable to air and moisture, and are of relatively low toxicity and environmental impact. The reactions of boronic acids can be divided into two categories according to whether the boron-oxygen or the carbon-boron bonds are involved. Reactions involving the B-O bonds Boroxine formation Most boronic acids readily undergo dehydration to form cyclic trimeric anhydrides (boroxines) (Scheme 1). This tends to occur spontaneously at room temperature, so that it is difficult to obtain the acid free from the anhydride. Since in almost all cases, both will undergo the required reaction, they can usually be regarded as equivalent. Scheme 1 Boronate formation The ease with which boronic acids react with diols, with loss of water, to give cyclic boronic esters (boronates) has led to their application in a number of areas, especially in the carbohydrate field. Protection of diols One of the main applications of boronic acids has been as reagents for protection and derivatization of 1,2- and 1,3-diols as boronates (1,3,2-dioxaborolanes and 1,3,2-dioxa- borinanes), particularly in carbohydrate chemistry.1 These have been widely used as volatile derivatives for GC and GC-MS purposes. The boronate derivatives are formed simply by stirring the boronic acid and diol together at ambient temperature, by warming, or, if necessary, with azeotropic removal of water. Usually cleavage occurs readily under hydrolytic conditions, by exchange with a glycol,2 or by treatment with hydrogen peroxide.3 Hindered boronic esters, such as those of pinacol, may be relatively stable to hydrolysis, and can often be purified by chromatography. A useful application of boronate protection is in the osmium tetroxide catalysed cis-dihydroxylation of alkenes under anhydrous conditions in the presence of