Preparation of 1,1′-Oxy-bis(3,3-bis(trifluoromethyl)-3(1H)-1,2-benziodoxole) and 2-(N-(p-Toluenesulfonyl)imino)iodobenzylmethyl Ether

Abstract

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Photoactivated N‐Acyliminoiodinanes Applied to Amination: an ortho‐Methoxymethyl Group Stabilizes Reactive Precursors

“…Interestingly,t he distance between the iodine atom of 3c and the carbonyl oxygen atom of the N-trifluoroacetyl group was also within the sum of the Va n der Waals radii, and 3c was obtained as am onomeric structure with no obvious intermolecular interactions; contrary to the previously reported X-ray structures of N-sulfonyliminoiodinanes. [6][7][8] TheN ÀIb ond length was 2.050 ,w hich is almost identical to that of N-iodosuccinimide (2.059 ), [22] and slightly longer than that of N-sulfonyliminoiodinanes (1.990-2.039 ). [6][7][8] Based on the X-ray structure of 3c,n atural population analysis was performed at the MP2/6-311 + G(d,p) level [23] using Gaussian 09.…”

“…[3,4] Because of their poor solubility in organic solvents,d erivatization to am ore soluble form by introducing an ortho-coordinating substituent has been developed. [5] As representative examples,i minoiodinanes bearing ortho-sulfonyl, [6] alkoxy, [7] and methoxymethyl [8] substituents,d eveloped by Protasiewicz, Zhdankin, and Woodward, respectively (Scheme 1a), improved the solubility,a nd those structures were successfully characterized by X-ray analyses.H owever,m ost of the reported N-protecting groups are limited to N-sulfonyl groups,s uch as tosyl and nosyl groups,a nd only one report has been made on the synthesis and reactivity of an N-acyliminoiodinane;p resumably because of their lability toward Hofmann rearrangement and/or hydrolysis. [9] In fact, although N-trifluoroacetyliminoiodinane 3a has been synthesized and reacted with an alkene under iron catalysis, 3a was reported to be unstable, [10] and the corresponding aziridine was only obtained in approximately 50 %y ield.…”

“…[6][7][8] TheN ÀIb ond length was 2.050 ,w hich is almost identical to that of N-iodosuccinimide (2.059 ), [22] and slightly longer than that of N-sulfonyliminoiodinanes (1.990-2.039 ). [6][7][8] Based on the X-ray structure of 3c,n atural population analysis was performed at the MP2/6-311 + G(d,p) level [23] using Gaussian 09. [24] Thec alculated charges of iodine,n itrogen, and the carbonyl oxygen were + 1.15, À0.81, and À0.80, respectively.…”

Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation

“…[53] This reaction worked efficiently at room temperature in a few minutes and didn't require any transition metals. In 2015, Waser and co-workers reported the synthesis of thiocyanates starting from thiols using cyanobenziodoxol(on)e reagents CBX (16) or CDBX (24) at room temperature (Scheme 22). [54] The reaction tolerated a wide range of functional groups such as halogens, nitro, amide, ethers, and esters and could be applied to both aromatic and aliphatic thiols.…”

“…[13] Hydroxy-and acetoxy derivatives 19-21 are key intermediates for the synthesis of other reagents. Most methods to access 19-21 involve the formation of chloride 13 and 14 by oxidation with tert-butyl hypochlorite [14] or cyanuric acid trichloride, [15] followed by hydrolysis [14,16] or acetolysis with silver acetate. [5a] EBX reagents bearing the trifluoromethyl groups can be accessed with Zhdankin's method using trimethylsilyl alkynes and trimethylsilyl triflate, [8b] whereas dimethyl-based reagents require the use of more reactive lithium acetylides.…”