Diborane reagents

The first organometallic Pd(III) complexes (44-46) were reported in 2006 (Fig. 25) [98]. Complexes 44 47 have been used as precatalysts for both the diborylation of terminal olefins and diborylation/cross-coupling tandem reactions (Fig. 26) [99]. The role of the Pd(III) complexes in these reactions has not been established the diborane reagents employed have been shown to immediately reduce the dinuclear Pd(III) complexes to Pd(II) species, and thus the Pd(III) complexes may be a precatalyst for lower-valent active catalysts. 

Synthesis by high-dilution techniques requires slow admixture of reagents ( 8-24 hrs) or very large volumes of solvents 100 1/mmol). Fast reactions can also be carried out in suitable flow cells (J.L. Dye, 1973). High dilution conditions have been used in the dilactam formation from l,8-diamino-3,6-dioxaoctane and 3,6-dioxaoctanedioyl dichloride in benzene. The amide groups were reduced with lithium aluminum hydride, and a second cyclization with the same dichloride was then carried out. The new bicyclic compound was reduced with diborane. This ligand envelops metal ions completely and is therefore called a cryptand (B. Dietrich, 1969). 

Diborane is the more electrophilic of the two reagents and while LiAH-14 often... 

Boron trifluoride is used for the preparation of boranes (see Boron compounds). Diborane is obtained from reaction with alkafl metal hydrides organoboranes are obtained with a suitable Grignard reagent. 

LiBH4 or NaBH4, Me3SiCl, THF, 24 h, 88-95%. This combination of reagents also reduces all functional groups that can normally be reduced with diborane.-... 

The most successful of the Lewis acid catalysts are oxazaborolidines prepared from chiral amino alcohols and boranes. These compounds lead to enantioselective reduction of acetophenone by an external reductant, usually diborane. The chiral environment established in the complex leads to facial selectivity. The most widely known example of these reagents is derived from the amino acid proline. Several other examples of this type of reagent have been developed, and these will be discussed more completely in Section 5.2 of part B. 

Diakyl carbamyl chlorides Diakyl aluminum hydrides Diborane Dibromoketone Dichloromethyl chloroformate Diphosgene Fuming nitric acid Gngnard reagents Hydrides nonvolatile... 

Diborane occupies a special place because all the other boranes can be prepared from it (directly or indirectly) it is also one of the most studied and synthetically useful reagents in the whole of chemistry.B2H6 gas can most conveniently be prepared in small quantities by the reaction of I2 on NaBH4 in diglyme [(MeOCH2CH2)20], or by the reaction of a solid tetrahydroborate with an anhydrous acid ... 

On the other hand, the observed syn preference of 59a is consistent with a study of hydroboration of 59a with diborane by Schueler and Rhodes [127], who obtained a mixture of the monoalcohols (symanti = 74 26) upon oxidative work-up. A similar magnitude of. yyn-preference was found (syn anti = 73 27) in the hydroboration with a bulkier borane, 2,3-dimethyl-2-butylborane (thexyl borane) [127]. This lack of effect of the bulk of the reagent in the hydroboration of 59a is consistent with the idea that the n face of 59a is free from steric bias [127], and that the syn preference of 59a found in dihydroxylation and epoxidation is non-sterically determined [128]. 

As is true for most reagents, there is a preference for approach of the borane from the less hindered face of the alkene. Because diborane itself is a relatively small molecule, the stereoselectivity is not high for unhindered alkenes. Table 4.4 gives some data comparing the direction of approach for three cyclic alkenes. The products in all cases result from syn addition, but the mixtures result from both the low regioselectivity and from addition to both faces of the double bond. Even 7,7-dimethylnorbornene shows only modest preference for endo addition with diborane. The selectivity is enhanced with the bulkier reagent 9-BBN. 

Reaction of the salts of primary and secondary alky Initio compounds with diborane in THF solution at 25 °C yields the corresponding hydroxylamines.117 Kabalka has reported the reduction of nitroalkenes to hydroxylamines or amines with a variety of borane and borohydride reagents (Eq. 6.61).118... 

Hydroboration, the addition of a boron-hydrogen bond across an unsaturated moiety, was first discovered by H. C. Brown in 1956. Usually, the reaction does not require a catalyst, and the borane reagent, most commonly diborane (B2H6) or a borane adduct (BH3-THF), reacts rapidly at room temperature to afford, after oxidation, the /AMarkovnikov alkene hydration product. However, when the boron of the hydroborating agent is bonded to heteroatoms which lower the electron deficiency, as is the case in catecholborane (1,3,2-benzodioxaborole) 1 (Scheme 1), elevated temperatures are needed for hydroboration to occur.4 5... 

In presence of boron trifluoride, the reagent is used to obtain diborane in situ. 

Boron Reagents Diborane, boron trifluoride, dialkyl borinates, aryl boronic acids. 

A distinction between silanol groups and adsorbed free water was attempted by Shapiro and Weiss (200a) and Weiss et al. (200b) using the reaction with diborane. Diborane reacts with free water with evolution of six moles of hydrogen per mole of consumed reagent ... 

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