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Synthesis and Properties of Ortho-T-Buso2c6h4-Substituted Iodonium Ylides

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Synthesis and Properties of Ortho-T-Buso2c6h4-Substituted Iodonium Ylides crystals Communication CommunicationSynthesis and Properties of ortho-t-BuSO2C6H4-Substituted Synthesis and Properties of ortho-t-BuSO C H -Substituted Iodonium Ylides 2 6 4 Iodonium Ylides Tomohiro Kimura 1, Shohei Hamada 2, Takumi Furuta 2, Yoshiji Takemoto 1,* and Yusuke Kobayashi 2,* Tomohiro Kimura 1, Shohei Hamada 2, Takumi Furuta 2, Yoshiji Takemoto 1,* and Yusuke Kobayashi 2,* 1 Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan; 1 Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan; [email protected] [email protected] 2 Department of Pharmaceutical Chemistry, Kyoto Pharmaceutical University, Kyoto 607-8414, Japan; 2 Department of Pharmaceutical Chemistry, Kyoto Pharmaceutical University, Kyoto 607-8414, Japan; [email protected] (S.H.); [email protected] (T.F.) [email protected] (S.H.); [email protected] (T.F.) * Correspondence: [email protected] (Y.T.); [email protected] (Y.K.); * Correspondence: [email protected] (Y.T.); [email protected] (Y.K.); Tel.: +81-75-753-4528 (Y.T.); +81-75-595-4666 (Y.K.) Tel.: +81-75-753-4528 (Y.T.); +81-75-595-4666 (Y.K.) Abstract:Abstract: Iodonium ylides ylides have have recently recently attracted attracted much much attention attention on on account account of oftheir their synthetic synthetic ap- applications.plications. However, However, only only a alimited limited number number of of repo reportsrts concerning concerning the properties andand reactivityreactivity ofof iodoniumiodonium ylidesylides exist,exist, whichwhich isis partlypartly duedue toto theirtheir instability.instability. InIn thisthis study,study, we we synthesized synthesized several several iodoniumiodonium ylidesylides that that bear bear both both an an electron-withdrawing electron-withdrawing group group and and an an aromatic aromatic ring ring with with an anortho ortho-t-- t-BuSO2 group. Based on the crystal structures of the synthesized iodonium ylides in combination BuSO2 group. Based on the crystal structures of the synthesized iodonium ylides in combination with natural-bond-orbitalwith natural-bond-orbital (NBO) (NBO) calculations, calculations, we estimated we estimated the strength the strength of the intra-of the andintra- intermolecular and intermo- halogen-bondinglecular halogen-bonding interactions. interactions. In addition, In addition, we investigated we investigated the reactivity the reac oftivity theiodonium of the iodonium ylides underylides photoirradiation.under photoirradiation. Keywords: halogen bonding; hypervalent iodine; NBO analysis; photochemistry; radical reactions Keywords: halogen bonding; hypervalent iodine; NBO analysis; photochemistry; radical reactions Citation: Kimura, T.; Hamada, S.; Furuta,Citation: T.; Kimura, Takemoto, T.;Y.; Hamada, Kobayashi, S.; Y. SynthesisFuruta, T.; and Takemoto, Properties Y.; of Kobayashi, 1.1. IntroductionIntroduction Y. Synthesis and Properties of ortho-t-BuSO2C6H4-Substituted IodoniumIodonium ylides,ylides, aa classclass ofof hypervalenthypervalent iodineiodine compoundscompounds [[1],1], havehave attractedattracted muchmuch Iodoniumortho- t-BuSO Ylides.2C6HCrystals4-Substituted2021, 11 , attentionattention duedue toto theirtheir useuse asas carbenecarbene precursorsprecursors forfor C-H-insertionC‒H-insertion and and cyclopropanation cyclopropanation 1085.Iodonium https://doi.org/10.3390/ Ylides. Crystals 2021, 11, x. reactionsreactions (Scheme (Scheme1a) 1a) [ 2 ,[2,3].3]. Moreover, Moreover, iodonium iodonium ylides ylides have have been been used used for various for various synthetic syn- cryst11091085https://doi.org/10.3390/xxxxx applications,thetic applications, including including condensations condensations with thioamides with thioamides to produce to produce thiazole ringsthiazole in aqueous rings in mediaaqueous (Scheme media1 (Schemeb; Nu = 1b; thioamide) Nu = thioamide) [4,5], and [4,5], for and the for introduction the introduction of 18F of atoms 18F atoms into AcademicAcademic Editors: Editor: Sergiy RosokhaRosokha, − aromaticinto aromatic rings rings (Scheme (Scheme1c; Nu 1c;= Nu F )[ = 6F,−7)]. [6,7]. It has It alsohas also been been reported reported that that depending depending on the on andAtash Atash V. Gurbanov V. Gurbanov iodoniumthe iodonium ylide ylide and nucleophileand nucleophile that is that employed, is employed, the equilibrium the equilibrium between between the T-shaped the T- intermediatesshaped intermediates A and B canA and be influencedB can be influenc [6,7], anded thus,[6,7], theand ratio thus, of couplingthe ratio productsof coupling C Received:Received: 2020 August August 2021 2021 and D can be controlled. Accepted:Accepted: 3 3 September September 2021 2021 products C and D can be controlled. Published:Published: 7 7 September September 2021 2021 Publisher’sPublisher’s Note: Note:MDPI MDPI stays stays neutral neu- withtral regardwith toregard jurisdictional to jurisdictional claims in publishedclaims in published maps and maps institutional and institu- affil- iations.tional affiliations. Copyright: © 2021 by the authors. Copyright:Submitted for© 2021possible by theopen authors. access Licenseepublication MDPI, under Basel, the terms Switzerland. and con- Thisditions article of the is Creative an open Commons access article At- distributedtribution (CC under BY) license the (http://crea- terms and conditions of the Creative Commons tivecommons.org/licenses/by/4.0/). Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ Scheme 1. General synthetic utility of iodonium ylides. (a) Cyclopropanation of alkenes (b) Introduction 4.0/). of nucleophile into active methylene compound (c) Introduction of nucleophile into aromatic rings. Crystals 2021, 11, x. https://doi.org/10.3390/xxxxx www.mdpi.com/journal/crystals Crystals 2021, 11, 1085. https://doi.org/10.3390/cryst11091085 https://www.mdpi.com/journal/crystals Crystals 2021, 11, x FOR PEER REVIEW 2 of 7 Scheme 1. General synthetic utility of iodonium ylides. (a) Cyclopropanation of alkenes (b) Intro- Crystals 2021, 11, 1085 duction of nucleophile into active methylene compound (c) Introduction of nucleophile2 of 7 into aro- matic rings However, to date, only a limited number of reports concerning the properties and However, to date, only a limited number of reports concerning the properties and reactivity of iodonium ylides have been published, which is at least in part due to their reactivity of iodonium ylides have been published, which is at least in part due to their instability (e.g.,instability degradation (e.g., via degradation intermediates via intermediates A and/or B) onA and/or account B) of on the account remaining of the remaining σ- σ-hole of intermediateshole of intermediates A and B, which A and can B, reactwhich with can nucleophilesreact with nucleophiles such as water. such We as water. We an- anticipate thatticipate the synthesis that the of asynthesis variety of of iodonium a variety ylidesof iodonium and the ylides investigation and the ofinvestigation their of their properties wouldproperties provide would essential provide information essential for informatio the advancementn for the ofadvancement synthetic applica- of synthetic applica- tions such as chemoselectivetions such as chemoselective coupling reactions. coupling Of particular reactions. interest Of particular to us are interest iodonium to us are iodonium ylides that containylides a coordinatingthat contain aortho coordinatinggroup on ortho the aromatic group on ring the[ aromatic8], as such ring groups [8], as are such groups are known to stabilizeknown iodonium to stabilize ylides iodonium and other ylides hypervalent and othe iodiner hypervalent compounds iodine[5 –compounds9], thus [5–9], thus increasing theirincreasing solubility their via intramolecular solubility via intramolecular halogen bonding halogen (XB) [ bonding10]. In this (XB) study, [10]. we In this study, we synthesized severalsynthesized iodonium several ylides iodonium bearing bothylides an bearing electron-withdrawing both an electron-withdrawing group and an group and an 2 aromatic ring witharomatic an ortho ring- twith-BuSO an2 grouportho-t-BuSO [8,11]. Basedgroup on [8,11]. the crystalBased structureson the crystal of the structures of the synthesized iodoniumsynthesized ylides iodonium in combination ylides in with combination natural-bond-order with natural-bond-order (NBO) analysis, (NBO) we analysis, we also estimatedalso the strengthestimated of the the strength intra- and of intermolecularthe intra- and intermolecular XBs [12–23]. In XBs addition, [12–23]. we In addition, we investigated theinvestigated reactivity of the these reactivity iodonium of these ylides iodoni underum photoirradiation ylides under photoi [24–27rradiation]. [24–27]. 2. Results 2. Results We began by synthesizingWe began by iodonium synthesizi ylidesng iodonium2 via the ylides condensation 2 via the of condensation iodosobenzene of iodosobenzene 1 [11] with a variety1 [11] ofwith active a variety methylene of active compounds methylene (Table compounds1). The reaction (Table 1). of The1 and reaction the of 1 and the ◦ active methyleneactive compounds methylene proceeded compounds at 0proceededC in etheric at 0 solvents°C in etheric such solvents as THF such or Et 2asO THF or Et2O to to furnish thefurnish corresponding the corresponding iodonium ylidesiodonium (2) as ylides precipitates (2) as precipitates
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