Recent Advances in Hypervalent Iodine Chemistry

Abstract

In recent years, an explosive growth of reactivities of hypervalent iodine reagents has witnessed and these reagents, featuring facile availability and easy handleness, offer multiple advantages over establised methods as an efficient multipurpose oxidants, whose reactivities are similar to derivatives of mercury, chromium, lead, thallium and other heavy metals, but without the toxicity and environmental problems of these heavy metal agents. Thus, hypervalent iodine reagents have received much more attention from the synthetic chemists. This account mainly summarizes our recent research progress in the area of hypervalent iodine chemistry, especially focusing on the excellent performances and unique applications brought about by the new hypervalent iodine reagents and new combinations of them both developed in our group: (1) first utilization of a recyclable iodine(III) reagent iodosodilactone for the direct esterification, amidation and peptide synthesis and high efficient liquid-phase oligo-peptide synthesis mediated by a more powerful iodosodilactone-type reagent, 6-(3,5-bis-(trifluoromethyl)phenyl)-1H,4H-2aλ 3 -ioda-2,3-dioxacyclopenta[hi]indene-1,4-dione (FPID); (2)

Copper(I)-Catalyzed Intramolecular Asymmetric Double C-Arylation for the Formation of Chiral Spirocyclic Bis-oxindoles

“…In 2012, Du and Zhao reported a synthesis of racemic spirocyclic bis-oxindoles from N 1 , N 3 -diarylmalonamides through a PIFA­[PhI-(TFA) 2 ]-promoted intramolecular oxidative coupling (Scheme a). , In 2014, Gong and co-workers developed such reactions further, achieving an elegant catalytic asymmetric version with chiral iodoarenes and oxidants (Scheme b) . However, because of the incompatibility of some functional groups with oxidative conditions and the complexity of reactions mediated by iodine reagents, serious limitations and challenges to these synthetic efforts still persisted, including limited substrate scope, moderate reaction efficiency, and poor regioselectivity . Further efforts may also be needed for further improvement of the enantioselectivity of such reactions.…”

A Benziodoxole-Based Hypervalent Iodine(III) Compound Functioning as a Peptide Coupling Reagent

“…Hypervalent iodine reagents have attracted considerable attention of synthetic chemists due to their rich reactivities, low toxicity, ready, availability, and recyclability (Varvoglis, 1997;Zhdankin andStang, 2002, 2008;Wirth, 2005;Brown et al, 2013;Singh and Wirth, 2014;Zhdankin, 2014;Duan et al, 2016;Li et al, 2016;Yoshimura and Zhdankin, 2016;Han and Zhang, 2018;Liu et al, 2019). In 2012, we first reported that iodosodilactone, a bicyclic benziodoxole compound, could function as a coupling reagent to promote the efficient syntheses of esters, macrocyclic lactones, amides, and peptides in the presence of PPh 3 at 60 o C (Scheme 1) (Tian et al, 2012).…”

Hypervalent-Iodine-Mediated Formation of Epoxides from Carbon(sp2)–Carbon(sp3) Single Bonds

“…Hypervalent iodine reagents, due to their safety, ready availability, environmental friendliness, and regenerability, are preferred organo-oxidants in the organic synthesis . In this study, as part of our ongoing exploration of the reactivity of AIBX (5-trimethylammonio-1,3-dioxo-1,3-dihydro-1λ 5 -benzo­[ d ]­[1,2]­iodoxol-1-ol anion), a water-soluble hypervalent iodine­(V) reagent that was first synthesized in our laboratory, we developed an efficient method for oxidative formation of epoxide groups directly from C sp2 –C sp3 single bonds in a single step using AIBX as an oxidant in the absence of a catalyst (Figure E).…”