A Triazole‐Substituted Aryl Iodide with Omnipotent Reactivity in Enantioselective Oxidations

Abstract

A widely applicable triazole‐substituted chiral aryl iodide is described as catalyst for enantioselective oxidation reactions. The introduction of a substituent in ortho‐position to the iodide is key for its high reactivity and selectivity. Besides a robust and modular synthesis, the main advantage of this catalyst is the excellent performance in a plethora of mechanistically diverse enantioselective transformations, such as spirocyclizations, phenol dearomatizations, α‐oxygenations, and oxidative rearrangements. DFT‐calculations of in situ generated [hydroxy(tosyloxy)iodo]arene isomers give an initial rational for the observed reactivity.

Electrophilic Vinylation of Thiols under Mild and Transition Metal‐Free Conditions

“…The reactivity of iodine(III) compounds can be influenced by ortho-substituents, [22] and EBX reagents with substituted benziodoxolone cores have been investigated. [23] Hence, a series of novel, substituted VBX derivatives were synthesized using Nachtsheims procedure. [11a, 21] Electronic factors were investigated through 2 b-2 e with p-substituted benziodoxolone cores, and steric effects were screened with osubstituted VBX 2 f, 2 g ( Table 2).…”

Recent discoveries on the structure of iodine(iii) reagents and their use in cross-nucleophile coupling

“…This is also showcased by the ongoing interest in the development of new iodine(III) and iodine(V) compounds. 119,[158][159][160][161] The use of ketones and their derivatives is particularly interesting, because the 2e À oxidation gives rise to an a-carbocationic ketone synthon, which prone to undergo carbocationic rearrangements. This will continue to inspire chemists to design new sequences and serve as an engine for serendipitous discovery.…”

Iodolopyrazolium Salts: Synthesis, Derivatizations, and Applications

“…[52][53][54] Our group is interested in the synthesis and reactivity of N-heterocyclic stabilized iodanes (NHIs) as well as their monovalent iodoarenes as pre-catalysts. [55][56][57][58][59] Recently, we investigated several hydroxy(tosyloxy) species as oxidants, including C-and Nbound pyrazole and indazole derivatives. [57,58] Herein, we want to report the synthesis of cyclic, pyrazole-substituted iodolium salts (benzo [4,5]iodolo [3,2-c]pyrazol-4-ium (bis)triflates) and their versatile utilization as intermediates for pyrazole functionalization strategies as well as their application as potent halogen bonding (XB) donors.…”