43 research outputs found
Enantiospecific sp(2)-sp(3) coupling of secondary and tertiary boronic esters
The cross-coupling of boronic acids and related derivatives with sp² electrophiles (the SuzukiâMiyaura reaction) is one of the most powerful CâC bond formation reactions in synthesis, with applications that span pharmaceuticals, agrochemicals and high-tech materials. Despite the breadth of its utility, the scope of this Nobel prize-winning reaction is rather limited when applied to aliphatic boronic esters. Primary organoboron reagents work well, but secondary and tertiary boronic esters do not (apart from a few specific and isolated examples). Through an alternative strategy, which does not involve using transition metals, we have discovered that enantioenriched secondary and tertiary boronic esters can be coupled to electron-rich aromatics with essentially complete enantiospecificity. As the enantioenriched boronic esters are easily accessible, this reaction should find considerable application, particularly in the pharmaceutical industry where there is growing awareness of the importance of, and greater clinical success in, creating biomolecules with three-dimensional architectures
CCDC 909044: Experimental Crystal Structure Determination
An entry from the Cambridge Structural Database, the worldâs repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures
CCDC 909045: Experimental Crystal Structure Determination
An entry from the Cambridge Structural Database, the worldâs repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures
Reactivity of Lewis Acid Activated Diaza- and Dithiaboroles in Electrophilic Arene Borylation
Hydride abstraction from <i>N,N</i>â˛-bisÂ(adamantyl)<sub></sub>-1-hydrido-1,3,2-benzodiazaborole with catalytic [Ph<sub>3</sub>C]Â[<i>closo</i>-CB<sub>11</sub>H<sub>6</sub>Br<sub>6</sub>] resulted in a low yield of arene borylation and a major product
derived from migration of both adamantyl groups to the arene backbone.
In contrast, the related aryl-substituted diazaborole <i>N,N</i>â˛-(2,6-diisopropylphenyl)-1-bromo-1,3,2-diazaborole did not
borylate benzene or toluene, being resistant to halide abstraction
even with strong halide acceptors: e.g., [Et<sub>3</sub>Si]Â[<i>closo</i>-CB<sub>11</sub>H<sub>6</sub>Br<sub>6</sub>]. The reactivity
disparity arises from greater steric shielding of the boron p<sub><i>z</i></sub> orbital in the 2,6-diisopropylphenyl-substituted
diazaboroles. Boron electrophiles derived from 1-chloro-1,3,2-benzodithiaborole
((CatS<sub>2</sub>)ÂBCl) are active for arene borylation, displaying
reactivity between that of catecholato- and dichloro-boron electrophiles.
[(CatS<sub>2</sub>)ÂBÂ(NEt<sub>3</sub>)]Â[AlCl<sub>4</sub>] is significantly
less prone to nucleophile-induced transfer of halide from [AlCl<sub>4</sub>]ÂŻ to boron compared to catecholato<i> </i> and dichloro borocations, enabling it to borylate arenes containing
nucleophilic âNMe<sub>2</sub> moieties in high conversion (e.g., <i>N,N</i>,4-trimethylaniline and 1,8-bisÂ(dimethylamino)Ânaphthalene).
Calculations indicate that the magnitude of positive charge at boron
is a key factor in determining the propensity of chloride transfer
from [AlCl<sub>4</sub>]ÂŻ to boron on addition of a nucleophile
Reactivity of Lewis Acid Activated Diaza- and Dithiaboroles in Electrophilic Arene Borylation
Hydride abstraction from <i>N,N</i>â˛-bisÂ(adamantyl)<sub></sub>-1-hydrido-1,3,2-benzodiazaborole with catalytic [Ph<sub>3</sub>C]Â[<i>closo</i>-CB<sub>11</sub>H<sub>6</sub>Br<sub>6</sub>] resulted in a low yield of arene borylation and a major product
derived from migration of both adamantyl groups to the arene backbone.
In contrast, the related aryl-substituted diazaborole <i>N,N</i>â˛-(2,6-diisopropylphenyl)-1-bromo-1,3,2-diazaborole did not
borylate benzene or toluene, being resistant to halide abstraction
even with strong halide acceptors: e.g., [Et<sub>3</sub>Si]Â[<i>closo</i>-CB<sub>11</sub>H<sub>6</sub>Br<sub>6</sub>]. The reactivity
disparity arises from greater steric shielding of the boron p<sub><i>z</i></sub> orbital in the 2,6-diisopropylphenyl-substituted
diazaboroles. Boron electrophiles derived from 1-chloro-1,3,2-benzodithiaborole
((CatS<sub>2</sub>)ÂBCl) are active for arene borylation, displaying
reactivity between that of catecholato- and dichloro-boron electrophiles.
[(CatS<sub>2</sub>)ÂBÂ(NEt<sub>3</sub>)]Â[AlCl<sub>4</sub>] is significantly
less prone to nucleophile-induced transfer of halide from [AlCl<sub>4</sub>]ÂŻ to boron compared to catecholato<i> </i> and dichloro borocations, enabling it to borylate arenes containing
nucleophilic âNMe<sub>2</sub> moieties in high conversion (e.g., <i>N,N</i>,4-trimethylaniline and 1,8-bisÂ(dimethylamino)Ânaphthalene).
Calculations indicate that the magnitude of positive charge at boron
is a key factor in determining the propensity of chloride transfer
from [AlCl<sub>4</sub>]ÂŻ to boron on addition of a nucleophile