Synthesis of Hypervalent Iodine(III) Reagents Containing a Transferable (Diarylmethylene)amino Group and Their Use in the Oxidative Amination of Silyl Ketene Acetals

Abstract

12 58 5l 6l [a] Reactionsw ere performedo na0.4 mmol scale. Yields are isolated yields. The isolated products contained asmall amount of dimers of 5. See the SupportingInformation for details. [b] Reaction was conducted at RT.[ c] E/Z ratios were not determined. Scheme 2. Oxidative amination using hypervalentiodine reagents 3 and 4.Scheme 3. Synthesis of aprimary amine through aone-pot procedure.

Recent Advances and the Prospect of Hypervalent Iodine Chemistry

“…For instance, Kiyokawa and Minakata et al synthesized an aryl-λ 3 -iodane containing a transferable (diarylmethylene)amino group in 2019, which could be applied to the oxidative amination of silyl ketene acetals affording the corresponding α-amino esters (Scheme 3a). 14 In 2020, our group reported the first trifluoromethylthio-λ 3 -iodane reagent TFTI and its synthetic utility for the oxidative trifluoromethylthiolation of various nucleophiles (Scheme 3b). 15 Scheme 3.…”

Synthesis, Characterization of Spirocyclic λ3‐Iodanes and Their Application to Prepare 4,1‐Benzoxazepine‐2,5‐diones and 1,3‐Diynes

“…For example, the cyclic iodine(III) (called as λ 3 ‐iodane) containing acetate, halogens, trifluoromethyl, azides, cyanides, aryl and alkyl groups, [1h, 2] were reported by the pioneering groups, such as, Waser, Zhdankin, Kita, Beringer, Koser, Valvoglis, Moriarty, Ochiai, and Togni [1, 2] . More recently, two type of cyclic λ 3 ‐iodanes containing a (diarylmethylene)amino and nitrooxy groups were reported by the group of Kiyokawa, Minakata [2e] and Katayev, [2f] respectively.…”

5-(Diarylimino)- and 5-(sulfoximido)dibenzothiophenium triflates: syntheses and applications as electrophilic aminating reagents

“…In addition, single electron transfer to 1 or 3 should deliver dibenzothiophene and N-center radicals, as in the case of the analogous I(III)-compounds. 8,9 Reactivity studies Once compounds 1a-c and 3a-f were completely characterized, their potential as electrophilic amination reagents was preliminarily examined. Our study started with an attempt to prepare sulfenylimines 6 by direct reaction of 3a-f with thiols under mildly basic conditions.…”

“…5 Much more obscure is the chemistry of sulfonium salts bearing nitrogen-based substituents. Specifically, while many hypervalent iodine reagents containing transferable nitrogen functional groups such as azido, 6 phthalimido, 7 diarylimino, 8 or sulfoximido are available, 9 only a few S-analogues of these compounds have been reported to date and the studies regard-ing their reactivity are even more scarce. 10 We speculated however that they should also share similarities with their iodine counterparts and hypothesized that imino-and sulfoximido-substituted sulfonium salts might potentially function as electrophilic aminating reagents or efficient sources of imine/sulfoximide radicals (Scheme 1b).…”