Synthesis and reactivity of six‐membered cyclic diaryl λ3‐bromanes and λ3‐chloranes

Bhattacherjee, Dhananjay, Kariuki, Benson M. ORCID: https://orcid.org/0000-0002-8658-3897, Piscelli, Bruno A., Cormanich, Rodrigo A. and Wirth, Thomas ORCID: https://orcid.org/0000-0002-8990-0667 2025. Synthesis and reactivity of six‐membered cyclic diaryl λ3‐bromanes and λ3‐chloranes. Angewandte Chemie , e202424559. 10.1002/ange.202424559

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Abstract

Despite the remarkable advancements in hypervalent iodine chemistry, exploration of bromine and chlorine analogues remains in its infancy due to their difficult synthesis. Herein, we introduce six‐membered cyclic λ3‐bromanes and λ3‐chloranes. Through single‐crystal X‐ray structural analyses and conformational studies, we delineate the crucial bonding patterns pivotal for the thermodynamic stability of these compounds. Notably, these investigations reveal pronounced π‐π stacking phenomena within the crystal lattice of hypercoordinated bromine(III) and chlorine(III) species. Their reactivity profile is explored as they are radical precursors or electrophilic reagents in metal‐free intermolecular biaryl couplings, O‐ and S‐arylations, and Cu(I)‐promoted intramolecular biaryl couplings which is complementary to the known reactivity of five‐membered bromanes and chloranes. Mechanistic insights are provided, elucidating the pathways governing their reactivity and underscoring the potential in organic synthesis.

Item Type:	Article
Date Type:	Published Online
Status:	In Press
Schools:	Chemistry
Additional Information:	License information from Publisher: LICENSE 1: URL: http://onlinelibrary.wiley.com/termsAndConditions#vor, Start Date: 2025-01-17
Publisher:	Wiley
ISSN:	0044-8249
Date of Acceptance:	16 January 2025
Last Modified:	29 Jan 2025 16:05
URI:	https://orca.cardiff.ac.uk/id/eprint/175679

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