Hypervalent Iodine Reagents for the Oxidation of Alcohols and Their Application to Complex Molecule Synthesis

Abstract

Hypervalent iodine(V) derivatives such as 2-iodoxybenzoic acid (IBX) and Dess±Martin periodinane [DMP; 1,1,1-tris(acetyloxy)-1,1-dihydro-1,2-benziodoxol-3-(1H)-one] have been used widely for the oxidation of alcohols to aldehydes and ketones during the last decade because of their high chemoselectivity, mild reactivity, and high yielding process. This review focuses on the recent progress in the oxidation of alcohols to carbonyl compounds using IBX, DMP, and other hypervalent iodine reagents, and their application to total syntheses of a variety of complex natural products.

A visible-light-promoted radical reaction system for azidation and halogenation of tertiary aliphatic C–H bonds

“…In 1996, Zhdankin8 reported that the reaction of simple hydrocarbons with azidoiodane 1 in the presence of benzoyl peroxide led to the selective azidation of 3° and activated 2° C–H bonds in moderate to good yield 9–11. Hartwig recently discovered that Fe/PyBOX catalysts promote aliphatic C–H azidation with 1 under milder conditions, allowing the labeling of complex natural products with high selectivity 12,13.…”

Organo‐Iodine(III)‐Catalyzed Oxidative Phenol–Arene and Phenol–Phenol Cross‐Coupling Reaction

“…[2b] Am ajor reason for this side reaction is the difficulty associated with the tunable reactivity of phenols by controlling their oxidation potential using aprotecting group for the phenol hydroxy group.T herefore,t he development of an efficient catalytic cross-coupling of unprotected phenols for the construction of biaryl compounds is still highly desirable.R ecently,W aldvogel and co-workers reported an electrochemical phenolarene cross-coupling reaction using boron-doped diamond electrodes. [10][11][12][13][14][15] Inspired by these studies,wenow report abroadly applicable organoiodine(III)-catalyzed oxidative cross-coupling reaction of phenols using Oxone as aterminal oxidant (Scheme 1). [9] While recent metal-catalyzed cross-couplings of phenols have been studied, the organocatalytic cross-coupling reaction still remains particularly challenging.R ecently,w e developed the oxidative cross-coupling reaction of aromatic compounds using hypervalent iodine reagents.…”

Concise synthesis of functionalized benzocyclobutenones

“…LiTMP was used as the base to generate the corresponding benzyne, 20 and acetaldehyde enolate was produced in situ from n -BuLi and THF. While previous studies took acetaldehyde enolate as the limiting reagent, 17, 18 we found higher yield of benzocyclobutenol 7a was obtained when aryl bromide 6a was used as the limiting reagent (entry 2).…”