Photoactivated <i>N</i>‐Acyliminoiodinanes Applied to Amination: an <i>ortho</i>‐Methoxymethyl Group Stabilizes Reactive Precursors

Kobayashi, Yusuke; Masakado, Sota; Takemoto, Yoshiji

doi:10.1002/anie.201710277

Cited by 71 publications

(35 citation statements)

References 69 publications

(61 reference statements)

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“…Crystallographic parameters of the intra-and intermolecular XB interactions in the crystals of iodonium ylides 2e and 2g. Finally, we investigated the reactivity of the synthesized iodonium ylides under photoirradiation conditions (Scheme 2) [9,[24][25][26][27]. When ylide 2a and ten equivalents of Nmethylpyrrole were irradiated at 365 nm, the active methylene group was introduced at the C2 position of N-methylpyrrole in 61% yield (Scheme 2a).…”

Section: Resultsmentioning

confidence: 99%

“…Based on the crystal structures of the synthesized iodonium ylides in combination with natural-bond-order (NBO) analysis, we also estimated the strength of the intra-and intermolecular XBs [12][13][14][15][16][17][18][19][20][21][22][23]. In addition, we investigated the reactivity of these iodonium ylides under photoirradiation [24][25][26][27].…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Properties of ortho-t-BuSO2C6H4-Substituted Iodonium Ylides

et al. 2021

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Iodonium ylides have recently attracted much attention on account of their synthetic applications. However, only a limited number of reports concerning the properties and reactivity of iodonium ylides exist, which is partly due to their instability. In this study, we synthesized several iodonium ylides that bear both an electron-withdrawing group and an aromatic ring with an ortho-t-BuSO2 group. Based on the crystal structures of the synthesized iodonium ylides in combination with natural-bond-orbital (NBO) calculations, we estimated the strength of the intra- and intermolecular halogen-bonding interactions. In addition, we investigated the reactivity of the iodonium ylides under photoirradiation.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and Properties of ortho-t-BuSO2C6H4-Substituted Iodonium Ylides

et al. 2021

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“…Examples of known iodonium imides 3 include N-tosyl-, 28 N-methanesulfonyl, 29 N-triflyl, 30,31 and Ntrifluoroacetyl derivatives. 32,33 34,35 Several phenyliodonium imides 6 derived from heteroarenesulfonylamides and other precursors have been synthesized from (diacetoxyiodo)benzene 4 and the respective amides 5 (Scheme 2). Imides 6 can be used as sources of the corresponding heterocycle-containing nitrenes in copper-catalyzed aziridination and sulfimidization reactions.…”

Section: Methodsmentioning

confidence: 99%

“…Single crystal X-ray structural data have been reported for the following iodonium imides presented in Figure 1: phenyl(N-tosylimino)iodane 12, 28 mesityl(N-tosylimino)iodane 13, 28 o-tolyl(N-tosylimino)iodane 14, 41 orthosulfonyl substituted phenyliodonium imide 8, 39 ortho-methoxy substituted phenyliodonium imide 15, 40 orthomethoxymethyl substituted iodonium imides 16, 42 17, 33 and 18, 33 nitro substituted phenyliodonium imides 19 and 20, 35 and (N-triflylimino)iodane 21. 30 Aryl(N-tosylimino)iodanes in general have a linear polymeric, asymmetrically bridged structure with the Tshaped geometry around the iodine centers.…”

Section: Structural Studiesmentioning

confidence: 99%

Iodonium imides in organic synthesis

Yoshimura¹,

Yusubov²,

Zhdankin³

2019

Arkivoc

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Iodonium imides (ArINR) represent an important class of hypervalent iodine(III) compounds recently emerging as versatile, efficient and environmentally friendly synthetic reagents with numerous applications in academic and industrial research. Iodonium imides, which are also known as iminoiodanes, are widely used in organic synthesis as common nitrene precursors in the aziridination of alkenes and the amidation reactions of various organic substrates. In the present review, the preparation and structural features of iminoiodanes are discussed, and recent developments in their synthetic applications are summarized.

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“…To solve thesep roblems, we focusedo nt he effects of ortho substituents on the solubility and stability of iodonium ylides [14b, 17] and hypervalent iodine compounds. [18] The introduction of an ortho substituent would decrease side reactionsb y blockingo ne of the s-holes, and the cis-selective coordination of thioamide to the iodonium ylide would promote the CÀS bond formation (Scheme 1B,E qns 7a nd 8). In particular, the introduction of an ortho nitrog roup would enhance the reactivity of the correspondingp recursor,A rI III (OAc) 2 ,w hich would enable condensations with various active methylene compounds under mild conditions to produce iodoniumy lides with broad functional group tolerance (Scheme 1B,E qn 6).…”

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Divergent and Chemoselective Transformations of Thioamides with Designed Carbene Equivalents

Saito

Kobayashi

Takemoto

2019

Chemistry A European J

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The reactions of thioamides with ortho-nitrosubstituted iodonium ylides proceededu nder mild conditions to give enaminones or thiazoles, depending on the iodonium ylide used. Thisp rotocol allowed the use of protic solvents, includinga queous solutions, and therefore coupling reactions with complex molecules such as peptides or steroids were possible. Am ilda nd efficient methodf or thes ynthesis of various iodonium ylides was established. DFT calculations suggested that the halogen bondingb etween at hioamidea nd iodonium ylide was important in this chemoselective coupling reaction. The potential use of enaminones conjugated with pharmaceuticals as prodrugs was also demonstrated.Thioamides have attracted much attention because they are isosteres of amides, butw ith higherl ipophilicities and stabilities. Many studies of peptides and proteins with thioamide moieties have been conducted. [1] An increasing number of methods for the introduction of thioamides at desiredp ositions of peptides are being developed. [2] In addition,t hioamides have high nucleophilicities and their selectivet ransformations have recently been studied. [3] In particular,t he reactions of thioamide groups, whicha re rarely found in biomolecules, have potential applicationsi nc hemoselective bioconjugation,w hich is one of the most important tools for drug discoverya nd in chemical biology. [4,5] However,o nly af ew examplesofs uch reactions have been reported. These reports include transition-metal-catalyzed coupling reactions with carbene equivalents. [5] Use of diazomalonates as carbene precursors gave enaminones (Scheme 1A,E qn 1), [5d-f] whereast hiazoles were obtained when a-diazo ketoesters were used as the carbene precursors( Scheme 1A,E qn 2). [5b,c] Both products were supposedly obtained through CÀSb ond formation. Althoughe naminones [6] and thiazoles [7] are both attractive pharmacophores with specificp roperties, these reactions generally requireh igh temperatures because of the formation of inert complexes through thioamide coordination to the metal catalyst. It is therefore difficult to apply these reactions to heatlabile molecules such as proteins. Undesired OÀHi nsertion [8] of metalc arbenoids into polar solvents such as alcohols also prevents thioamideu se with complex molecules, whicha re difficult to dissolve in non-polar solvents.Herein, we report ah ighly chemoselective couplingr eaction of varioust hioamides with av ariety of carbene equivalents in ap rotic solventu nder mild conditions. Iodonium ylides (Scheme 1A,E qns 3a nd 4) were selected as carbene equivalents [9] because hypervalenti odine compounds, including iodonium ylides, have recently been reported to have s-holes, [10] and they are expectedt of orm halogenb onds (XB) [11,12] selectively with soft Lewis bases [13] such as thioamides, even in the presence of ap olar functional group such as an alcohol. However,t he use of iodonium ylides as electrophiles (Scheme 1A, Eqn 4) has been less studied [14,15] than metal carbenoid precur-Scheme1.Summary of t...

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

Cited by 71 publications

References 69 publications

Synthesis and Properties of ortho-t-BuSO2C6H4-Substituted Iodonium Ylides

Synthesis and Properties of ortho-t-BuSO2C6H4-Substituted Iodonium Ylides

Iodonium imides in organic synthesis

Divergent and Chemoselective Transformations of Thioamides with Designed Carbene Equivalents

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