Regioselektive Photoisomerisierung/C‐C‐Bindungsbildung von asymmetrischem B(ppy)(Mes)(Ar): die Rolle von Arylgruppen am Boratom

Af ully reversible photothermal isomerization between carborane-fused trigonal-planar azaborole (darkpurple) and tetrahedral borirane (pale-yellow) has been observed, leading to the isolation and structural characterization of the first example of carborane-fused borirane.DFT calculations indicate that the azaborole is thermodynamically more stable than the borirane by 11.2 kcal mol À1 ,a nd the energy barrier for the thermal conversion from azaborole to borirane is 35.5 kcal mol À1 .The reactivity studies show that the BÀC(cage) bond in borirane can be broken in the reaction with CuCl, HCl, or elemental sulfur. Scheme 1. Photothermal transformations of four-coordinate organoboranes.Scheme 2. Photothermal isomerization between 1 and 2.

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Reversible Photothermal Isomerization of Carborane‐Fused Azaborole to Borirane: Synthesis and Reactivity of Carbene‐Stabilized Carborane‐Fused Borirane

Wang

Zhang

Xie

2017

Angewandte Chemie

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Photochemical Intramolecular C−H Addition of Dimesityl(hetero)arylboranes through a [1,6]‐Sigmatropic Rearrangement

et al. 2017

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An ew reaction mode for triarylboranes under photochemical conditions was discovered. Photoirradiation of dimesitylboryl-substituted (hetero)arenes produced spirocyclic boraindanes,where one of the C À Hbonds in the ortho-methyl groups of the mesityl substituents was formally added in asyn fashion to aC À Cd ouble bond of the (hetero)aryl group. Quantum chemical calculations and laser flash photolysis measurements indicated that the reaction proceeds through a[ 1,6]-sigmatropic rearrangement. This behavior is reminiscent of the photochemical reaction mode of arylalkenylketones,t hus demonstrating the isosteric relation between tricoordinate organoboron compounds and the corresponding pseudo-carbocationic species in terms of pericyclic reactions. Despite the disrupted p-conjugation, the resulting spirocyclic boraindanes exhibited ac haracteristic absorption band at relatively long wavelengths (l = 370-400 nm).

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Ring Expansion, Photoisomerization, and Retrocyclization of 1,4,2‐Diazaboroles

Ganguly

et al. 2017

Angewandte Chemie

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Regioselektive Photoisomerisierung/C‐C‐Bindungsbildung von asymmetrischem B(ppy)(Mes)(Ar): die Rolle von Arylgruppen am Boratom

Cited by 31 publications

References 30 publications

Reversible Photothermal Isomerization of Carborane‐Fused Azaborole to Borirane: Synthesis and Reactivity of Carbene‐Stabilized Carborane‐Fused Borirane

Reversible Photothermal Isomerization of Carborane‐Fused Azaborole to Borirane: Synthesis and Reactivity of Carbene‐Stabilized Carborane‐Fused Borirane

Photochemical Intramolecular C−H Addition of Dimesityl(hetero)arylboranes through a [1,6]‐Sigmatropic Rearrangement

Ring Expansion, Photoisomerization, and Retrocyclization of 1,4,2‐Diazaboroles

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