Pseudocyclic Arylbenziodoxaboroles: Efficient Benzyne Precursors Triggered by Water at Room Temperature. Issue 66 (7th November 2017)

• Record Type: Journal Article
• Authors: Yoshimura, Akira; Fuchs, Jonathan M.; Middleton, Kyle R.; Maskaev, Andrey V.; Rohde, Gregory T.; Saito, Akio; Postnikov, Pavel S.; Yusubov, Mekhman S.; Nemykin, Victor N.; Zhdankin, Viktor V.
• Is Part Of: Chemistry. Volume 23:Issue 66(2017)
• Page Start: 16738
• Page End: 16742
• Publication Date: 2017-11-07
• Subjects: arynes -- benzyne -- hypervalent iodine -- iodine -- iodonium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201704393
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: New organohypervalent iodine compounds, arylbenziodoxaborole triflates, were prepared from 1‐acetoxybenziodoxaboroles and arenes by treatment with trifluoromethanesulfonic acid under mild conditions. Single crystal X‐ray crystallography of these compounds revealed a pseudocyclic structure with a short intramolecular interaction of 2.698 to 2.717 Å between oxygen and iodine in the benziodoxaborole ring. These new pseudocyclic aryliodonium salts readily generate aryne intermediates upon treatment with water at room temperature. The generated aryne intermediates react with various substrates to give the corresponding aryne adducts in moderate to good yields. Furthermore, the new benzyne precursors can also work as arylating reagents towards aromatic rings. The aryne intermediates generated from arylbenziodoxaborole triflates selectively react with tert ‐butyl phenol forming products of ortho arylation in moderate yields. Abstract : New hypervalent iodine compounds : Preparation and X‐ray structures of novel pseudocyclic arylbenziodoxaborole triflates are reported. These compounds readily generate aryne intermediates upon treatment with water at room temperature.