Catalysts with boron—hydrogen bonds

A potential way to avoid the formation of undesired side products, like in 7.2., is the use of such boron compounds that have only one transferable group. In most cases boronic acids are the compounds of choice, as they are easy to prepare, insensitive to moisture and air, and usually form crystalline solids. In certain cases, however the transmetalation of the heteroaryl group might be hindered by the formation of stable hydrogen bonded complexes. In such cases the use of a boronate ester, such as in equation 7.4., provides better yields. For example pyridine-2-boronic acid dimethylester coupled readily with a bromoquinoline derivative under conditions similar to 7.3. (potassium hydroxide was used as base and tetrabutylammonium bromide as phase transfer catalyst).6... 

The location of the catalyst is a problem in all attempts at kinetic measurement in these systems. It is well known that boron fluoride forms 1 1 complexes with most oxygenated compounds and 1 2 complexes when hydroxyl groups are present. The ternary complexes are to be regarded as a form of oxonium salt in which the third molecule is held by hydrogen bonding, so in the present reaction mixtures, equilibria of the type... 

We have found that chiral boronate complexes with BLA (Brpnsted acid-assisted chiral Lewis acids) to give new catalysts for enantioselective synthesis which achieve selectivity by a double effect of intramolecular hydrogen-bonding interaction and attractive ji-ti donor-acceptor interaction in the transition state by a hydroxy aromatic group [27a],... 

The treatment of solutions of platinum metals with aqueous borohydride results in the formation of finely divided black precipitates that are active catalysts for alkene hydrogenations. The platinum black obtained in this way was twice as active as that obtained by the hydrogenation of platinum oxide. The borohydride reduced rhodium black is even more active. While the borohydride reduction of base metals gives the corresponding metal borides, there is little, if any, boron incorporated into these platinum metal blacks. Analysis of the borohydride reduced palladium found that while the palladium boron ratio in the bulk was 10 1, less than 1% of the surface was boron.59 7, 5 small amount of boron, however, can impart a significant difference in catalytic activity to this catalyst as compared with other, more common, palladium catalysts. The most striking difference is the inability of the borohydride reduced palladium to promote the hydrogenolysis of activated C-0 and C-N bonds, a reaction that takes place readily over standard palladium catalysts. 

Shortly afterward, the same authors also developed a palladium(II) catalyst [Pd(2-PyCH=NPh)(OCOC6F5)2] for the hydroarylation of fullerene with boronic acids, which presents good catalytic activity (reaction generally occurring at room temperature), bench stability in the solid state, and efficiency under air conditions. Single-crystal X-ray diffraction analysis confirmed unequivocally the addition of the aryl moiety and hydrogen in a 1,2-fashion at the a double bond of Cjq, with the phenyl group attached at the position close to the pole of the C70 unit [31]. 

The arylation of carbon-hydrogen bonds in polycyclic aromatic hydrocarbons, using aryl boron compoimds or aryl silanes, may be achieved with a palladium acetate/o-chloranil catalyst. The Suzuki-Miyaura reaction involves palladium-catalysed coupling of an arylboronic acid with an aryl hahde in the presence of base. After oxidative addition of palladium to the hahde, reaction with base may form intermediates such as (105). Transmetalation with the boronic acid followed by reductive elimination yields... 

Yamamoto developed a conceptually new class of chiral boron-Lewis acids 174 (Equation 20) that can readily be assembled from a tetraphenol ligand and B(OMe)3 [93, 94]. These were shown to be especially effective with a wide range of a-substituted enals in enantioselective Diels-Alder reactions. One illustrative example is the cycloaddition between aldehyde 173 and cyclopentadiene to give 175 in 99% ee, > 99 1 exo/endo selectivity, and quantitative yield [93]. Yamamoto suggested that these catalysts 174 were Bransted-assisted chiral Lewis acids (termed BLAs), in which the phenol proton activates the enal substrates by hydrogen bonding, as depicted in the proposed transition state assembly 176. 

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