Boron oxidative addition

Boron, oxide additives in silicate-based glasses, x-ray photomission spectroscopic spectra. 151/ Bridges... 

Allylation with allyl borates takes place smoothly under neutral conditions. Allylic alcohols are also used for allylation in the presence of boron oxide by in situ formation of allylic borates[125]. Similarly, arsenic oxide is used for allylation with allylic aleohols[126]. In addition, it was claimed that the allyl alkyl ethers 201. which are inert by themselves, can be used for the allylation in the presence of boron oxide[127]. 

The boronic acid 2 is first converted to an activated species 8 containing a tetravalent boron center by reaction with a base. Halides or triflates (OTf = trilluoromethanesulfonate) are used as coupling partners R-X for the boronic acids. In many cases the rate-limiting step is the oxidative addition. With respect to the leaving group X, the rate decreases in the order ... 

Table 1. Boron- -Cobalt Compounds by Oxidative Addition Reactions ...

A special kind of oxidative addition occurs between phosphine cobalt hydride complexes and boron halides ... 

A special type of oxidative addition takes place between cobaltocene and boron halides (MeBBr2, PhBCl2, BCI3, BBr3) . Treatment of cobaltocene in hexane or... 

This reaction typifies the two possibilities of reaction routes for M-catalyzed addition of an S-X (or Se-X) bond to alkyne (a) oxidative addition of the S-X bond to M(0) to form 94, (b) insertion of alkyne into either the M-S or M-X bond to provide 95 or 96 (c) C-X or C-S bond-forming reductive elimination to give 97 (Scheme 7-21). Comparable reaction sequences are also discussed when the Chalk-Harrod mechanism is compared with the modified Chalk-Harrod mechanism in hydrosily-lations [1,3]. The palladium-catalyzed thioboratiori, that is, addition of an S-B bond to an alkyne was reported by Miyaura and Suzuki et al. to furnish the cis-adducts 98 with the sulfur bound to the internal carbon and the boron center to the terminal carbon (Eq. 7.61) [62]. 

These reactions proceed with retention of double-bond configuration in both the boron derivative and the alkenyl halide. The oxidative addition by the alkenyl halide, transfer... 

Recently, Larock and coworkers used a domino Heck/Suzuki process for the synthesis of a multitude of tamoxifen analogues [48] (Scheme 6/1.20). In their approach, these authors used a three-component coupling reaction of readily available aryl iodides, internal alkynes and aryl boronic acids to give the expected tetrasubsti-tuted olefins in good yields. As an example, treatment of a mixture of phenyliodide, the alkyne 6/1-78 and phenylboronic acid with catalytic amounts of PdCl2(PhCN)2 gave 6/1-79 in 90% yield. In this process, substituted aryl iodides and heteroaromatic boronic acids may also be employed. It can be assumed that, after Pd°-cata-lyzed oxidative addition of the aryl iodide, a ds-carbopalladation of the internal alkyne takes place to form a vinylic palladium intermediate. This then reacts with the ate complex of the aryl boronic acid in a transmetalation, followed by a reductive elimination. 

In relation to the mechanistic proposal, an interesting reactivity of (boryl)(silyl)platinum(n) complex has been reported.223 The complex is prepared by the reaction of silylborane with Pt(cod)2 complex via oxidative addition (Scheme 46). The (boryl)(silyl)platinum complex undergoes insertion of alkynes at the B-Pt bond to give (/3-borylalkenyl)(silyl)platinum(n) complex in high yield. Importantly, the insertion takes place regioselectively, with Pt-G bond formation at the internal. -carbon atom. This result may indicate that the boron-transition metal bond is more prone to undergo insertion of unsaturated molecules. 

Miyaura and co-workers reported the platinum-catalyzed diboration of allenes with bis(pinacolato)diboron (Scheme 16.52) [57]. The catalytic cycle involves a sequence of oxidative addition of bis(pinacolato)diboron to Pt(0), insertion of an allene into the B-Pt bond and reductive elimination of an allylic boronate, re-producing the Pt(0) species. (Z)-Allylic boronates are formed stereoselectively in the reaction with monosubstituted allenes, which strongly suggests a pathway via a vinylplatinum species rather than a Jt-allylplatinum species. 

Westcott et al. have also observed the exclusive Mnear product 3-02NC,5H4CH2CH2Bcat in the hydroboration of 3-nitrostyrene by [lrCl2(T -C5Me5)]2 and HBcat [45]. Similarly, the Hnear isomer 4-(Bcat)2NC6H4CH2CH2Bcat could be preferentially obtained in the iridium-mediated hydroboration of 4-vinylaniline as an example of a mild route to anihne derivatives containing boronate esters. Westcott et al. claimed a mechanism that may not necessarily proceed via conventional pathways that invoke initial oxidative addition of HBcat to the metal center. 

Repeated exposure of rats to an aerosol at a concentration of 470mg/m for 10 weeks caused only mild nasal irritation repeated exposure of rats to 77mg/m for 23 weeks resulted in elevated creatinine and boron content of the urine in addition to increased urinary volume. Conjunctivitis resulted when the dust was applied to the eyes of rabbits, probably the result of the exothermic reaction of boron oxide with water to form boric acid topical application of boron oxide dust to the clipped backs of rabbits produced erythema that persisted for 2-3 days. ... 

The rate of silicate sol and gel formation is pH and water-alcohol-sensitive as is the solubility of the amorphous silica that is formed. Silica networks are based on (Si04) " tetrahedra modified by (O3 Si-O, M+) units and often addition of boron oxide, aluminum oxide, titanium IV oxide, or zirconium IV oxide. 

The overall mechanism is closely related to that of the other cross-coupling methods. The aryl halide or triflate reacts with the Pd(0) catalyst by oxidative addition. The organoboron compound serves as the source of the second organic group by transmetala-tion. The disubstituted Pd(II) intermediate then undergoes reductive elimination. It appears that either the oxidative addition or the transmetalation can be rate-determining, depending on reaction conditions.134 With boronic acids as reactants, base catalysis is normally required and is believed to involve the formation of the more reactive boronate anion.135... 

Various preparative methods are adopted at nonstoichiometric formulations, incomplete dehydration or using oxide additives to obtain boron phosphate of varying purity for its catalytic applications. The compound also forms hydrates (tri- tetra-, penta-, and hexahydrates) which readily decompose in water to phosphoric acid and boric acid. 

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