Unknown

Dataset Information

0

1,2-Azaborine's Distinct Electronic Structure Unlocks Two New Regioisomeric Building Blocks via Resolution Chemistry.


ABSTRACT: Two new 1,2-azaborine building blocks that enable the broad diversification of previously not readily accessible C4 and C5 ring positions of the 1,2-azaborine heterocycle are developed. 1,2-Azaborine's distinct electronic structure allowed the resolution of a mixture of C4- and C5-borylated 1,2-azaborines. The connection between the electronic structure of C4 and C5 positions of 1,2-azaborine and their distinct reactivity patterns is revealed by a combination of reactivity studies and kinetic measurements that are supported by DFT calculations. Specifically, we show that oxidation by N-methylmorpholine N-oxide (NMO) is selective for the C4-borylated 1,2-azaborine, and the Ir-catalyzed deborylation is selective for the C5-borylated 1,2-azaborine via kinetically controlled processes. On the other hand, ligand exchange with diethanolamine takes place selectively with the C4-borylated isomer via a thermodynamically controlled process. These results represent the first examples for chemically distinguishing a mixture of two aryl mono-Bpin-substituted isomers.

SUBMITTER: McConnell CR 

PROVIDER: S-EPMC6609151 | biostudies-literature | 2019 Jun

REPOSITORIES: biostudies-literature

altmetric image

Publications

1,2-Azaborine's Distinct Electronic Structure Unlocks Two New Regioisomeric Building Blocks via Resolution Chemistry.

McConnell Cameron R CR   Haeffner Fredrik F   Baggett Andrew W AW   Liu Shih-Yuan SY  

Journal of the American Chemical Society 20190523 22


Two new 1,2-azaborine building blocks that enable the broad diversification of previously not readily accessible C4 and C5 ring positions of the 1,2-azaborine heterocycle are developed. 1,2-Azaborine's distinct electronic structure allowed the resolution of a mixture of C4- and C5-borylated 1,2-azaborines. The connection between the electronic structure of C4 and C5 positions of 1,2-azaborine and their distinct reactivity patterns is revealed by a combination of reactivity studies and kinetic me  ...[more]

Similar Datasets

| S-EPMC9292521 | biostudies-literature
| S-EPMC2686302 | biostudies-literature
| S-EPMC8156644 | biostudies-literature
| S-EPMC9322044 | biostudies-literature
| S-EPMC4347638 | biostudies-literature
| S-EPMC7317810 | biostudies-literature
| S-EPMC3375708 | biostudies-literature
| S-EPMC6968937 | biostudies-literature
| S-EPMC6013930 | biostudies-literature
| S-EPMC7581296 | biostudies-literature