Development of Imino‐λ³‐iodanes with Improved Reactivity for Metal‐Free [2+2+1] Cycloaddition‐Type Reactions

Abstract

Aiming at the enhancement of electrophilicity of imino-l 3 -iodanes, we have developed (tosylimino)pentafluorophenyl-l 3 -iodane, which shows superior reactivity compared to the commonly used (tosylimino)phenyl-l 3 -iodane in the [2 + 2 + 1]-type synthesis of imidazoles.

An Inexpensive, Efficient Alternative to NADPH to Support Catalysis by Thermostable Cytochrome P450 Enzymes

“…Firstly, dichloroiodo‐2‐ nitrobenzene was synthesized from 1‐iodo‐2‐nitrobenzene using a liquid phase chlorination with a 1 : 1 mixture of concentrated nitric acid and hydrochloric acid as described by Obeid et al . The isolated product was then used for the synthesis of NO 2 ‐PhIO as described by Baba et al . which in turn served as the starting material for the synthesis of 2‐NO 2 ‐BAIB, as described by the same authors.…”

“…Step 3: a) Different solvents (A, B, C) can be tested to identify the solvent which least affects P450 activity. This in turn can be used in step 3b) to supply the OS stepwise at intervals established in step 2 using the OS concentration established in step 1. described by Obeid et al [20] The isolated product was then used for the synthesis of NO 2 -PhIO as described by Baba et al [21] which in turn served as the starting material for the synthesis of 2-NO 2 -BAIB, as described by the same authors. The 1 H NMR of 2-NO 2 -PhIO and 2-NO 2 -BAIB were identical to those reported in the literature.…”

Oxidative cycloaddition of hydroxamic acids with dienes or guaiacols mediated by iodine(III) reagents

“…As part of our research on the syntheses of heterocycles by iodine(III)-mediated/catalyzed oxidative cycloaddition reactions [ 17 – 19 ], we have found that iodine(III) reagents are effective in the oxidation of N–O bonds of oximes in the cycloaddition reaction of in situ formed nitrile oxides [ 20 – 21 ]. Although Adam and Bottke’s group have demonstrated that (diacetoxyiodo)benzene (DIB) and iodosylbenzene are applicable to the ene reactions of acylnitroso species derived from hydroxamic acids [ 22 ], the iodine(III)-mediated oxidative cycloaddition reaction of hydroxamic acids with dienes is still unknown.…”

Photo-Induced Aziridination of Alkenes with <i>N</i>-Sulfonyliminoiodinanes

“…Very recently, we have developed newly designed Nacyliminoiodinanes, which were found to be activated under photo-irradiation conditions and utilized as N-acylnitrene equivalent. 23) The coordination of the oxygen atom of orthosubstituent (-OMe, -CH 2 OMe) to the iodine atom seemed to be essential for the photo-activation of N-acyliminoiodinanes as well as N-sulfonyliminoiodinanes, and silyl enol ethers were successfully α-aminated using those iminoiodinanes under photo-irradiation. We envisioned that such ortho-substituted iminoiodinanes could be similarly applied to a photoinduced aziridination of alkenes without using any catalysts.…”

“…17,28) Importantly, the aliphatic alkene 3g was also applicable to the catalyst-free reaction to give aziridine 4g in 41% yield. Furthermore, the aziridines bearing different N-sulfonyl groups 5a-7a were successfully obtained in 50-68% yields using 2b, 23) 2c, 23) and 1d as nitrogen source, respectively, although newly synthesized iminoiodinanes 1b and 1c did not furnish the corresponding products because of their poor solubility in dichloromethane.…”