Synthesis of {CB11} Monocarborane Sulfonamides by B2‐Selective Rhodium‐Catalyzed B−H Activation DOI Open Access

Zehua Ye,

Jizeng Sun,

Yujie Jin

et al.

Helvetica Chimica Acta, Journal Year: 2023, Volume and Issue: 106(11)

Published: Sept. 28, 2023

Abstract The synthesis of monocarborane sulfonamides is reported. methodology relies on coupling the anionic {CB 11 } boron cluster to sulfonyl azides. Under rhodium catalysis and with assistance a pyridine or pyrimidine directing group at C1 position, undergoes B−H activation. Conditions have been identified that lead B2‐selective mono‐sulfonamidation concomitant loss N 2 . protocol requires no additional ligand, oxidant base enables B−N bond formation various azide inputs. new products possess structure [1‐(heteroaryl)‐2‐(NHSO Ar)−CB H 10 ] − fully characterized by NMR spectroscopy mass spectrometry. In addition, three solid state structures confirm particular B2 substitution pattern. Furthermore, stoichiometric reaction pyridinyl precursor Rh(III) affords cyclometalated complex direct B−Rh has also X‐ray crystallography.

Language: Английский

Chemistry of three-dimensional icosahedral boron clusters anions: closo-dodecaborate (2-) [B12H12]2- and carba-closo-dodecaborate(-) [CB11H12]- DOI
Lingyao Wang,

Yunjia Jiang,

Simon Duttwyler

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 516, P. 215974 - 215974

Published: June 8, 2024

Language: Английский

Citations

16
Borenium Ylide-Mediated 12-B Arylation of Carborane Anions DOI Creative Commons
Y Kitazawa,

Toshiki Inoue,

Yuta Koike

et al.

JACS Au, Journal Year: 2025, Volume and Issue: unknown

Published: March 24, 2025

Developing novel approaches for B-vertex modification is significant in the chemistry of icosahedral boron clusters. Here, we report a protocol transformation air-stable 12-aryliodonium carborane anions, which are readily accessible on gram scale from corresponding (diacetoxyiodo)arenes (ArI(OAc)2) and anion, to 12-aryl-carborane anions. Mechanistic studies support idea that 12-B arylation proceeds via intramolecular reductive C-B bond formation 12-borenium ylide, followed by rearomatization. The reaction under mild conditions air suitable one-pot synthesis without need purification B-B coupling at vertex affords dumbbell-type anion dimers. This offers an alternative approach B-C closo borates, complementing conventional cross-coupling approaches.

Language: Английский

Citations

0
Noncatalyzed Intramolecular B–N and B–O Cross-Coupling of “Inert” Carboranes Lead to the Formation of an Unusual Oxoborane, via Reversible Cluster C–B Bond Scission DOI

Sergio Lovera,

Aaron Gregory,

Katherine Espinoza Morelos

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 13, 2025

Polyhalogenated closo-12-vertex carborane anions are thought to be inert species incapable of participating in direct B-X substitution reactions. Here, we show that this is not true and such can easily coaxed into intramolecular cross-coupling cyclizations without the need for a catalyst. When cage C-tethered O N-heteroallylic generated, variety cyclized products formed high yield under mild conditions. Additionally, even neutral nucleophiles, as pyridine moiety, undergo facile chemistry these reactions dependent on countercation. Serendipitously, also found when attempted with acetamide derivatives, an unprecedented cluster C-B bond scission reaction occurs, producing oxoborane stabilized by multicentered bonding. Amazingly molecule protonated, leading reformation reorganization, process reversible.

Language: Английский

Citations

0
Synthesis of {CB11} Monocarborane Sulfonamides by B2‐Selective Rhodium‐Catalyzed B−H Activation DOI Open Access

Zehua Ye,

Jizeng Sun,

Yujie Jin

et al.

Helvetica Chimica Acta, Journal Year: 2023, Volume and Issue: 106(11)

Published: Sept. 28, 2023

Abstract The synthesis of monocarborane sulfonamides is reported. methodology relies on coupling the anionic {CB 11 } boron cluster to sulfonyl azides. Under rhodium catalysis and with assistance a pyridine or pyrimidine directing group at C1 position, undergoes B−H activation. Conditions have been identified that lead B2‐selective mono‐sulfonamidation concomitant loss N 2 . protocol requires no additional ligand, oxidant base enables B−N bond formation various azide inputs. new products possess structure [1‐(heteroaryl)‐2‐(NHSO Ar)−CB H 10 ] − fully characterized by NMR spectroscopy mass spectrometry. In addition, three solid state structures confirm particular B2 substitution pattern. Furthermore, stoichiometric reaction pyridinyl precursor Rh(III) affords cyclometalated complex direct B−Rh has also X‐ray crystallography.

Language: Английский

Citations

2