149832-59-7

Upstream product

• 149832-56-4 1,1-bis(9-borabicyclo{3.3.1}non-9-yl)propane 
• 100-52-7 benzaldehyde 
• 280-64-8 9-bora-bicyclo[3.3.1]nonane 
• 121157-71-9 (3,3-bis(9-borabicyclo{3.3.1}non-9-yl)propyl)triethylsilane 
• 17874-26-9 triethyl(propyn-1-yl)silane 
• 30089-00-0 9-octyl-9-bora-bicyclo[3.3.1]nonane 
• 21205-91-4 9-borabicyclo[3.3.1]nonane dimer 
• 100-51-6 benzyl alcohol 
• 74763-89-6 B-(cyclopentylmethyl)-9-BBN 

Relevant academic research and scientific papers

Organogermanium(II) Hydrides as a Source of Highly Soluble LiH

The reactions of monomeric C,N-chelated organogermanium(II) hydride L(H)Ge?BH3 with organolithium salts RLi yielded lithium hydrogermanatoborates (Li(THF)2{BH3[L(H)GeR]})2. Compound (Li(THF)2{BH3[L(H)GePh]})2 was used as a source of LiH for the reduction of organic C=O or C=N bonds in nonpolar solvents accompanied by the elimination of a neutral complex L(Ph)Ge?BH3. The interaction of (Li(THF)2{BH3[L(H)GePh]})2 with the polar C=O bond was further investigated by computational studies revealing a plausible geometry of a pre-reactive intermediate. The experimental and theoretical studies suggest that, although the Li atom of (Li(THF)2{BH3[L(H)GePh]})2 coordinates the C=O bond, the GeH fragment is the active species in the reduction reaction. Finally, benzaldehyde was reduced by a mixture of L(H)Ge?BH3 with PhLi in nonpolar solvents.

Synthesis of Methylenecycloalkanes from Cycloalkenes via Borane Chemistry

B-(Cycloalkylmethyl)-9-BBN derivates, now readily available through the homologation reaction, are convenient substrates for the synthesis of exocyclic methylene compounds.The method appears to be general.Moreover, since the synthesis proceeds from the cycloalkene, it provides a valuable alternative to the customary methylenation of carbonyl compounds by the Wittig and related procedures.The method also provides a clean synthesis of deuterium-labeled compounds without positional scrambling or loss of label.

Method for preparing organic borate compound

A method for preparing an organic borate compound relates to organic borate compounds, and is characterized in that a catalyst, a carbonyl compound or an alkynes compound and a boron hydride react in an organic solvent to obtain the organic borate compound, wherein the catalyst is an alkali metal hydroxide, which is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide and the like, and is preferably sodium hydroxide. A carbonyl group or a terminal alkyne group can be efficiently reduced at a low price. As the low-price alkali metal hydroxide is taken as the catalyst, the boron hydride is catalyzed and selectively added to C-O dual bonds or C-C three bonds to obtain corresponding alkoxyl or alkenyl borate. The yield of the organic borate compound can be up to 99%. The prepared organic borate compound is suitable for aldehyde, ketone or alkynes compound substrates.

Metal-free disproportionation of formic acid mediated by organoboranes

In the presence of dialkylboranes, formic acid can be converted to formaldehyde and methanol derivatives without the need for an external reductant. This reactivity, in which formates serve as the sole carbon and hydride sources, represents the first exam

Trans-vinylboranes from 9-borabicyclo[3.3.1]nonane through dehydroborylation

The hydroboration of 1-alkynes (1) was reinvestigated by 11B NMR under optimized conditions (THF, 18 h, 0°C) and found to provide trans-vinyl-9-BBN adducts (2) together with variable amounts of 1,1-diborylalkanes (3) depending both upon the excess of 1 employed and the nature of alkyne substitution. By contrast, the formation of 3 with 2 equiv of 9-BBN-H is quantitative. A new completely stereoselective route to 2 from 3 was discovered with its reaction with ArCHO in an electrocyclic process (p = 0.42). While analogous to the Midland reduction, the term dehydroborylation is introduced to emphasize the olefination aspect of the reaction. Compound 3a (R = Me) is smoothly dehydroborylated at 25°C with PhCHO following second-order kinetics. Competitive rate studies reveal its reaction to be slower than that of Alpineborane (7) (k7/k3a = 4.5) but faster than that of B-siamyl-9-BBN (6) (k6/k3a = 0.34). The value of the dehydroborylation approach to 2 and the advantages of using 9-BBN derivatives in vinylborane reactions are demonstrated with numerous examples. Thus, 1,8-nonadiyne is converted, through a bis(vinylborane) (11), to pure trans,trans-1,9-dideuterio-1,8-nonadiene (12). This transformation has not been previously possible for 9-BBN-H because of competitive dihydroboration. The dihydroboration of 1-(triethylsilyl)-1-propyne, after thermal isomerization and deuterolysis, affords trans-(3-deuterioallyl)silane (16), a most remarkable overall conversion. The insertion of aromatic aldehydes into 2 was further demonstrated to provide a convenient entry to trans-allylic alcohols. The selective oxidation of 2 with TMANO produces trans-alkenyl-9-oxa-10-borabicyclo[3.3.2]decanes, 18, which resist further reaction with ArCHO, oxidation in the atmosphere, and protonolysis. A 1→ 3 → 2 → 20 sequence was employed without the isolation of 2 in a one-pot Suzuki coupling with ArBr to provide trans-stilbenes (20, Ar = p-C6H4X, X = OMe (80%), NMe2 (60%)).

Kinetics of Reductions of Substituted Benzaldehydes with B-Alkyl-9-borabicyclononane (9-BBN)

Second-order rate constants for the reaction of B-n-octyl-9-BBN with para-substituted benzaldehydes were obtained.Electron-withdrawing groups on the benzaldehyde increase the rate of reduction.The rate constants correlate with ?+ (ρ +1.03).Relative rates for reduction of para-substituted benzaldehydes with B-3-pinanyl-9-BBN gave a ρ of +0.49.The relative rates are consistent with a hydride addition to the carbonyl carbon in the rate-determining step.Activation parameters were obtained for the reaction of three benzaldehydes with B-n-octyl-9-BBN.The major barrier to the reaction is entropy.The large negative entropies of activation (-43 to -49 eu) indicate a highly ordered transition state.It is postulated that an organoborane-carbonyl oxygen complex is an intermediate in the reduction.