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Syntheses and Study of a Pyrroline Nitroxide Condensed Phospholene Oxide and a Pyrroline Nitroxide Attached Diphenylphosphine

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Syntheses and Study of a Pyrroline Nitroxide Condensed Phospholene Oxide and a Pyrroline Nitroxide Attached Diphenylphosphine molecules Article Syntheses and Study of a Pyrroline Nitroxide Condensed Phospholene Oxide and a Pyrroline Nitroxide Attached Diphenylphosphine Mostafa Isbera 1, Balázs Bognár 1 , Ferenc Gallyas 2,3,4, Attila Bényei 5 ,József Jek˝o 6 and Tamás Kálai 1,4,* 1 Faculty of Pharmacy, Institute of Organic and Medicinal Chemistry, University of Pécs, Szigeti st. 12, H-7624 Pécs, Hungary; [email protected] (M.I.); [email protected] (B.B.) 2 Department of Biochemistry and Medical Chemistry, University of Pécs Medical School, H-7624 Pécs, Hungary; [email protected] 3 HAS-UP Nuclear-Mitochondrial Interactions Research Group, H-1245 Budapest, Hungary 4 János Szentágothai Research Center, University of Pécs, Ifjúság 20, H-7624 Pécs, Hungary 5 Department of Pharmaceutical Chemistry, University of Debrecen, Egyetem tér 1, H-4032 Debrecen, Hungary; [email protected] 6 Department of Chemistry, University of Nyíregyháza, Sóstói st. 31/B, H-4440 Nyíregyháza, Hungary; [email protected] * Correspondence: [email protected]; Tel.: +36-72-536-221 Abstract: The reaction of a diene nitroxide precursor with dichlorophenylphosphine in a McCor- mac procedure afforded 1,1,3,3-tetramethyl-5-phenyl-1,2,3,4,5,6-hexahydrophospholo[3,4-c]pyrrole- 5-oxide-2-oxyl. Lithiation of the protected 3-iodo-pyrroline nitroxide followed by treatment with Citation: Isbera, M.; Bognár, B.; chlorodiphenylphosphine after deprotection afforded (1-oxyl-2,2,5,5-tetramethyl-2,5-dihydro-1H- Gallyas, F.; Bényei, A.; Jek˝o,J.; Kálai, pyrrol-3-yl)diphenylphosphine oxide, and after reduction, (1-oxyl-2,2,5,5-tetramethyl-2,5-dihydro- T. Syntheses and Study of a Pyrroline 1H-pyrrol-3-yl)diphenylphosphine was realized, which was also supported by X-ray single crystal Nitroxide Condensed Phospholene diffraction measurements. This pyrroline diphenylphosphine derivative was converted to hexade- Oxide and a Pyrroline Nitroxide cylphosphonium salt, which is an analogue of antineoplastic agent, MITO-CP. Attached Diphenylphosphine. Molecules 2021, 26, 4366. Keywords: lithiation; McCormac reaction; nitroxides; protecting groups; reduction https://doi.org/10.3390/ molecules26144366 Academic Editor: M. Amparo F. Faustino 1. Introduction Heterocyclic nitroxide derivatives of piperidine pyrrolidine, pyrroline and imida- Received: 21 May 2021 zoline have found various applications [1,2]. Stable nitroxide (aminoxyl) free radicals Accepted: 14 July 2021 possess unique properties and reactivity, and despite decades of experience working with Published: 19 July 2021 them, accessing new scaffolds without affecting the free valence is a challenge for every synthetic chemist active in this field [3]. Sometimes nitroxide moieties require temporary Publisher’s Note: MDPI stays neutral protection [4,5] to avoid irreversible destruction during various chemical transformations. with regard to jurisdictional claims in Nitroxides have a wide range of applications; they are used as co-oxidants in organic published maps and institutional affil- chemistry, building blocks for magnetic materials, superoxide dismutase mimics, antipro- iations. liferative compounds, mediators of polymerization, redox active materials in batteries, magnetic resonance imaging (MRI), and electron paramagnetic resonance imaging (EPRI) contrast agents [1,2]. These various applications require numerous paramagnetic scaffolds adjusted to different utilizations. Our idea is to combine various phosphorus-containing Copyright: © 2021 by the authors. functional groups with nitroxides, which may offer fascinating possibilities for synthetic, Licensee MDPI, Basel, Switzerland. structural and biological studies and the utilization of these new compounds [6,7]. In This article is an open access article continuation of our interest in the synthesis of nitroxide-based phosphorus compounds, distributed under the terms and we have promoted the synthesis of phosphorus-containing heterocycles condensed with conditions of the Creative Commons pyrroline nitroxide and pyrroline nitroxide-diphenylphosphine and pyrroline nitroxide- Attribution (CC BY) license (https:// diphenylphosphine oxide compounds. Although similar nitroxides have been previously creativecommons.org/licenses/by/ reported with nitronyl nitroxides [8] and a phosphorus-containing heterocycle [9], our 4.0/). Molecules 2021, 26, 4366. https://doi.org/10.3390/molecules26144366 https://www.mdpi.com/journal/molecules MoleculesMolecules 20212021,, 2626,, xx FORFOR PEERPEER REVIEWREVIEW 22 ofof 1111 Molecules 2021, 26, 4366 2 of 10 beenbeen previouslypreviously reportedreported withwith nitronylnitronyl nitrnitroxidesoxides [8][8] andand aa phosphorus-containingphosphorus-containing heter-heter- approachocycleocycle [9],[9], described ourour approachapproach in the describeddescribed present work inin thethe might presentpresent open workwork a new mightmight route openopen for aa synthesizingnewnew routeroute forfor such syn-syn- novelthesizingthesizing types suchsuch of paramagnetic novelnovel typestypes ofof phosphorus-containing paramagneticparamagnetic phosphorus-containingphosphorus-containing compounds. compounds.compounds. 2.2.2. Results ResultsResults and andand Discussions discussionsdiscussions 2.1.2.1.2.1. Synthesis SynthesisSynthesis of ofof Paramagnetic ParamaParamagneticgnetic Phospholene PhospholenePhospholene Oxide OxideOxide AAA standardstandardstandard procedureprocedureprocedure tototo formformform phospholenephospholenephospholene oxideoxideoxide isisis McCormacMcCormacMcCormac cycloadditioncycloadditioncycloaddition at-at-at- temptedtemptedtempted fromfrom compound compound 1a1a [10][10][10 ] andand and dichlorophenylphosphinedichlorophenylphosphine dichlorophenylphosphine [11,12].[11,12]. [11,12 However,].However, However, thisthis this ad-ad- additionditiondition diddid did notnot givegivegive the thethe expected, expected,expected, isolable isolableisolable product. product.product. Proposing ProposingProposing the disruption thethe disruptiondisruption of the nitrox-ofof thethe idenitroxidenitroxide under theunderunder reaction thethe reactionreaction conditions conditionsconditions applied, applied,applied, we protected wewe protectedprotected nitroxide nitroxidenitroxide as an O -acetylasas anan OO derivative-acetyl-acetyl de-de- 1brivative[4]. Treatment 1b [4]. Treatment of compound of compound1b with dichlorophenylphosphine 1b with dichlorophenylphosphine in a three-week-long in a three- rivative 1b [4]. Treatment of compound◦ 1b with dichlorophenylphosphine in a three- reactionweek-longweek-long time reactionreaction in pentane timetime inin at pentanepentane 37 C enabled atat 3737 °C°C us enabledenabled to obtain usus toto compound obtainobtain compoundcompound2b after 2b hydrolysis2b afterafter hy-hy- O withdrolysisdrolysis a modest withwith aa 36% modestmodest yield. 36%36% Deprotection yield.yield. DeprotectionDeprotection of the -acetylofof thethe O groupO-acetyl-acetyl by groupgroup a catalytic byby aa amountcatalyticcatalytic of NaOMe, followed by oxidation of the N-hydroxylamine with MnO2, offered 1,1,3,3- amountamount ofof NaOMe,NaOMe, followedfollowed byby oxidationoxidation ofof thethe NN-hydroxylamine-hydroxylamine withwith MnOMnO2,2, offeredoffered tetramethyl-5-phenyl-1,2,3,4,5,6-hexahydrophospholo[3,4-c]pyrrole-5-oxide-2-oxyl 2a as 1,1,3,3-tetramethyl-5-phenyl-1,2,3,4,5,6-hexahydrophospholo[3,4-c]pyrrole-5-oxide-2-1,1,3,3-tetramethyl-5-phenyl-1,2,3,4,5,6-hexahydrophospholo[3,4-c]pyrrole-5-oxide-2- the first pyrroline nitroxide condensed phospholene oxide (Scheme1). Compound 2a was oxyloxyl 2a2a asas thethe firstfirst pyrrolinepyrroline nitroxidenitroxide condcondensedensed phospholenephospholene oxideoxide (Scheme(Scheme 1).1). Com-Com- reduced to its hydroxylamine derivative in situ in the NMR tube (see Section 3.1.) and in the poundpound 2a2a waswas reducedreduced toto itsits hydroxylaminehydroxylamine dederivativerivative inin situsitu inin thethe NMRNMR tubetube (see(see Sec-Sec- resulted 31P-NMR we found a single peak at 61.8 ppm and methylene protons as multiplets tiontion 3.1.)3.1.) andand inin thethe resultedresulted 3131P-NMRP-NMR wewe foundfound aa singlesingle peakpeak atat 61.861.8 ppmppm andand methylenemethylene 2.68–2.73 and 2.85–2.29 ppm with 2H–2H integrals, suggesting that compound 2a contains protonsprotons asas multipletsmultiplets 2.68–2.732.68–2.73 andand 2.85–2.292.85–2.29 ppmppm withwith 2H–2H2H–2H integrals,integrals, suggestingsuggesting thatthat an endocyclic double bond. compoundcompound 2a2a containscontains anan endocyclicendocyclic doubledouble bond.bond. SchemeSchemeScheme 1. 1.1. Synthesis SynthesisSynthesis of ofof a aa paramagnetic paramagneticparamagnetic phospholene phospholphospholeneene oxide oxideoxide via viavia the thethe McCormack McCormackMcCormack reaction. reaction.reaction. 2.2.2.2.2.2. Synthesis SynthesisSynthesis of ofof Pyrroline PyrrolinePyrroline Nitroxide NitroxideNitroxide Diphenylphosphine DiphDiphenylphosphineenylphosphine and andand Its ItsIts Phosphonium PhosphoniumPhosphoniumSalt SaltSalt AsAsAs triphenylphosphine triphenylphosphinetriphenylphosphine isis anan essential essential building building blockblock ofof mitochondria-targetedmitochondria-targeted mitochondria-targeted anti-anti- an- tioxidantsoxidantsoxidants andand and neoplasticneoplastic neoplastic agentsagents agents [13,14],[13,14], [13,14 ],e.g.,e.g., e.g., lipophiliclipophilic lipophilic triphenylphosphoniumtriphenylphosphonium triphenylphosphonium cations,cations, cations, wewe weaimedaimed
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