Oxidation Catalysis by an Aerobically Generated Dess–Martin Periodinane Analogue

Abstract

Hypervalent iodine(V) reagents,s uch as Dess-Martin periodinane (DMP) and 2-iodoxybenzoic acid (IBX), are broadly useful oxidants in chemical synthesis.D evelopment of strategies to generate these reagents from dioxygen (O 2 )would immediately enable use of O 2 as aterminal oxidant in ab road arrayo fs ubstrate oxidation reactions.R ecently we disclosed the aerobic synthesis of I(III) reagents by intercepting reactive oxidants generated during aldehyde autoxidation. In this work, aerobic oxidation of iodobenzenes is coupled with disproportionation of the initially generated I(III) compounds to generate I(V) reagents.T he aerobically generated I(V) reagents exhibit substrate oxidation chemistry analogous to that of DMP.T he developed aerobic generation of I(V) has enabled the first application of I(V) intermediates in aerobic oxidation catalysis.

Chemo- and regioselective benzylic C(sp3)–H oxidation bridging the gap between hetero- and homogeneous copper catalysis

“…Furthermore, formation of deleterious methyl ester 2a′ could be overcome if we succeed to eliminate DTBP. Intrigued by the captivating works on molecular oxygen by the Powers group ( Maity et al., 2018a , 2018b ), the Freakley group ( Agarwal et al., 2017 ), and others ( Sushkevich et al., 2017 ), we envisioned that the coupling of aerial oxygen as a terminal oxidant for this transformation would be synthetically sustainable and attractive. To investigate, a reaction of 1a with catalytic copper powder under the oxygen atmosphere PhCF 3 afforded 20% of the desired product (Entry 16, Table 1 ).…”

Progress in organocatalysis with hypervalent iodine catalysts

“…In another report, an iodine( v )-catalysed aerobic oxidation of secondary alcohols 81 to the corresponding ketones 82 was achieved in good to excellent yields catalysed by 2- tert -butylsulfonyl-iodobenzene 85 in the presence of n -butyraldehyde 86 and CoCl 2 ·6H 2 O (Scheme 21). 92 The role of CoCl 2 ·6H 2 O was to initiate the aldehyde-promoted aerobic oxidation of precatalyst 85 to generate the iodine( v ) species in situ . In case of aromatic secondary alcohols, both electron rich and electron deficient derivatives were tolerated.…”

Dess–Martin Periodinane-Mediated Oxidative Coupling Reaction of Isoquinoline with Benzyl Bromide

“…In recent decades, hypervalent iodine (V) reagents have become a powerful synthetic tool in organic chemistry [ 21 , 22 ]. In particular, DMP has been proven an effective oxidant to construct C-N bonds [ 23 ].…”