One-pot generation of benzynes from 2-aminophenylboronates via a Rh(ii)-catalyzed N–H amination/oxidation/elimination cascade process

Abstract

Rh(ii)-Nitrene-mediated N–H amination of 2-aminophenylboronates triggered a cascade of oxidation/elimination processes resulting in the generation of benzynes.

Biobased C6-Furans in Organic Synthesis and Industry: Cycloaddition Chemistry as a Key Approach to Aromatic Building Blocks

“…A broad scope of benzoannulated 7-oxanorbornenes can be obtained via this approach. The utilization of diarynes (Table ) and polycyclic arynes (Table ) leads to the formation of condensed polycyclic systems. …”

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

“…Similarly, o -bromoacetophenone derivatives were found to serve as aryne precursors, where t -BuOK was used as the activating reagent . Very recently, generation methods based on one-pot protocols were realized. − …”

Silica gel-induced aryne generation from o-triazenylarylboronic acids as stable solid precursors

“…The reaction of 1d and O-tert-butyldimethylsilyl (TBS)-protected zidovudine 3j provided 4aj in a significantly higher yield than that obtained in a previous study, with the added advantage of inexpensive and environmentally benign conditions (Scheme 4a). 8 2-Siloxy-1,3-diene 3k, which is sensitive to various conditions, was also applicable as an arynophile to provide [2 + 2] cycloadduct 4ak in 58% yield, while no evidence of [4 + 2] cycloaddition was observed.…”

“…7 We recently reported the development of a new methodology for aryne generation from o-aminophenylboronates via the in situ preparation of a new aryne precursor, namely, N-tosyldiazene A (Scheme 1b). 8 However, under the conditions implemented for the in situ preparation of unstable A, including the generation of reactive Rh(II)-nitrene species from Rh(II) catalyst and iminoiodinane (TsN = IMes), the only applicable arynophiles were found to be azides and furans. These results prompted us to design a more stable precursor based on A, not requiring in situ preparation.…”