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Reactions of an Isolable Dialkylsilylene with Aroyl Chlorides

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Reactions of an Isolable Dialkylsilylene with Aroyl Chlorides molecules ArticleArticle Reactions of an Isolable Dialkylsilylene with Aroyl ReactionsArticle of an Isolable Dialkylsilylene with Aroyl Chlorides.ReactionsChlorides. of A A anNew New Isolable Route Route Dialkylsilyleneto to Aroylsilanes Aroylsilanes with Aroyl Xu-QiongChlorides.Xu-Qiong Xiao, Xiao, Xupeng Xupeng A NewLiu, Liu, Qiong Qiong Route Lu, Lu, Zhifang Zhifang to Li LiAroylsilanes *, *, Guoqiao Guoqiao Lai Lai and and Mitsuo Mitsuo Kira Kira * * Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Xu-QiongKey Laboratory Xiao, Xupeng of Organosilicon Liu, Qiong Chemistry Lu, Zhifang and Material Li *, TechnologyGuoqiao Lai of Ministryand Mitsuo of Education, Kira * HangzhouHangzhou Normal Normal University, University, Hangzhou Hangzhou 311121, 311121, China; China; xqxiao [email protected]@hznu.edu.cn (X.-Q.X.); (X.-Q.X.); [email protected]@163.com Laboratory of Organosilicon (X.L.) (X.L.);; [email protected] [email protected] Chemistry and (Q.L.);Ma (Q.L.);terial [email protected] [email protected] Technology of Mini (G.L.) (G.L.)stry of Education, *Hangzhou * Correspondence:Correspondence: Normal University,[email protected] [email protected] Hangzhou 311121, (Z.L.); (Z.L.); China; [email protected] [email protected] [email protected] (M.K.); (M.K.); (X.-Q.X.); Tel.: +86-571-2886-7825 (Z.L.) [email protected].: +86-571-2886-7825 (X.L.) (Z.L.); [email protected] (Q.L.); [email protected] (G.L.) * AcademicCorrespondence: Editor: Derek [email protected] J. McPhee (Z.L.); [email protected] (M.K.); Academic Editor: Derek J. McPhee Received:Tel.: +86-571-2886-7825 14 September 2016;(Z.L.) Accepted: 8 October 2016; Published: 15 October 2016 Received: 14 September 2016; Accepted: 8 October 2016; Published: date AcademicAbstract: Editor:The reactions Derek J. McPhee of isolable dialkylsilylene 1 with aromatic acyl chlorides afforded aroylsilanes Abstract:Received:3a–3c exclusively. 14The September reactions Aroylsilanes 2016; of isolable Accepted3a dialkylsilylene–: 3c8 Octoberwere characterized 2016; 1 with Published: aromatic by date1H-, acyl 13 C-,chlorides and 29 Si-NMRafforded spectroscopy,aroylsilanes 3ahigh-resolution–3c exclusively. massAroylsilanes spectrometry 3a–3c were (HRMS), characterized and single-crystal by 1H-, 13C-, molecularand 29Si-NMR structure spectroscopy, analysis. high-resolutionAbstract:The reaction The reactions mechanisms mass spectrometry of isolable are discussed dialkylsilylene (HRMS), in comparison and 1 withsingle-crystal aromatic with related acylmolecular reactionchlorides structure of afforded1 with analysis. chloroalkanes aroylsilanes The reaction3aand–3cchlorosilanes. exclusively. mechanisms Aroylsilanes are discussed 3a– 3cin comparisonwere characterized with related by 1H-, reaction 13C-, and of 1 29withSi-NMR chloroalkanes spectroscopy, and chlorosilanes.high-resolution mass spectrometry (HRMS), and single-crystal molecular structure analysis. The reactionKeywords: mechanismsdialkylsilylene; are discussed silyl ketone; in comparison acylsilane; with insertion; relatedX-ray reaction analysis of 1 with chloroalkanes and Keywords:chlorosilanes. dialkylsilylene; silyl ketone; acylsilane; insertion; X-ray analysis Keywords: dialkylsilylene; silyl ketone; acylsilane; insertion; X-ray analysis 1. Introduction 1. IntroductionAcylsilanes or α-silyl ketones have been known as a unique class of silicon compounds [1–9], showing remarkably red–red shifted n!π* transition bands [1,2] and being useful as distinct reagents 1. IntroductionAcylsilanes or α-silyl ketones have been known as a unique class of silicon compounds [1–9], showingin organic remarkably synthesis [red–red4–6,10– 19shifted]. Most n→ ofπ all,* transition acyltris(trimethylsilyl)silanes bands [1,2] and being are useful of particular as distinct importance, reagents inwhich organicAcylsilanes were synthesis utilized or [4–6,10–19].α-silyl for the ketones synthesis Most have of ofall, been the acyltris firstknown(trimethylsilyl)silanes stable as a silicon–carbon unique class areof doubly silicon of particular bonded compounds importance, compounds [1–9], whichshowing(silenes) were remarkably [20 utilized,21]. However, forred–red the thesynthesis shifted synthesis n →ofπ the* of transition acylsilanesfirst stable bands issilicon–carbon still [1,2] limited and bein because doublyg useful ofbonded as the distinct relatively compounds reagents facile (silenes)insilicon–carbon organic [20,21]. synthesis bondHowever, [4–6,10–19]. cleavage the synthesis underMost of the all, of reaction acyltrisacylsilane(trimethylsilyl)silanes conditions.s is still limited The direct because are reaction of ofparticular the of arelatively silylmetal importance, facile with silicon–carbonwhichan acyl were halide utilized bond afforded cleavagefor the the synthesis correspondingunder the of reaction the acylsilanes,first cond stableitions. silicon–carbon but The the yieldsdirect reactiondoubly were usually bonded of a silylmetal low compounds due towith the an(silenes)undesired acyl halide [20,21]. secondary afforded However, reactions the the corresponding synthesis [22,23]. of The acylsilaneacylsila oxidationnes,s isbut of stillα the-silyl limited yields alcohols because were using usually of the ordinary relativelylow due oxidizing to facile the undesiredsilicon–carbonreagents oftensecondary bond leads cleavage toreactions the corresponding under [22,23]. the The reaction aldehydes oxidation cond [5 itions.].of The α-silyl firstThe successfulalcoholsdirect reaction using synthesis ofordinary a ofsilylmetal an aroylsilaneoxidizing with reagentsanwas acyl achieved halide often afforded byleads using to anthethe elaboratecorresponding corresponding two-step acylsila aldehy routenes, indes goodbut [5]. the yieldsThe yields first (Equation were successful usually (1)) [22synthesis low], while due ittoof is thean not aroylsilaneundesiredapplicable secondarywas for the achieved synthesis reactions by ofusing alkanoylsilanes.[22,23]. an elaborateThe oxidation two-step of α route-silyl inalcohols good yieldsusing (Equationordinary oxidizing(1)) [22], whilereagents it is oftennot applicable leads to forthe the corresponding synthesis of alkanoylsilanes. aldehydes [5]. The first successful synthesis of an aroylsilane was achieved by using an elaborate two-step route in good yields (Equation (1)) [22], while it is not applicable for the synthesis of alkanoylsilanes. (1)(1) The dithiane route applicable for the synthesis of a wider range of acylsilanes was studied(1) by The dithiane route applicable for the synthesis of a wider range of acylsilanes was studied by Brook et al. [24] and Corey et al. [25] at the same time in 1967 (Equation (2)). The defect of the method Brook et al. [24] and Corey et al. [25] at the same time in 1967 (Equation (2)). The defect of the method is theThe use dithianeof a toxic route mercury applicable compound for the for synthesisthe hydrolysis of a wider of the rangesilylated of acylsilanesdithianes. was studied by Brookis the et use al. of [24] a toxic and Corey mercury et al. compound [25] at the for same the hydrolysistime in 1967 of (Equation the silylated (2)). dithianes. The defect of the method is the use of a toxic mercury compound for the hydrolysis of the silylated dithianes. (2) A variety of acylsilanes have been synthesized up to date using different methods, the reactions(2)(2) of protected aldehydes, esters, and other carboxylic acid derivatives, etc. with various silicon reagents [1–9].A variety of acylsilanes have been synthesized up to date using different methods, the reactions of protectedDuring aldehydes,the course esters,of our and studies other of carboxylic the reaction acids derivatives,of an isolable etc. dialkylsilylenewith various silicon with reagentsvarious functional[1–9]. groups [26–30], we have found that the silylene inserts exclusively into the C–Cl bond of During the course of our studies of the reactions of an isolable dialkylsilylene with various MoleculesfunctionalMolecules 20162016 groups, 21, 21, 1376;, 1376; [26–30], doi:10.3390/molecules21101376 doi:10.3390/molecules21101376 we have found that the silylene inserts exclusivelywww.mdpi.com/journal/moleculeswww.mdpi.com/journal/molecules into the C–Cl bond of Molecules 2016, 21, 1376; doi:10.3390/molecules21101376 www.mdpi.com/journal/molecules Molecules 2016, 21, 1376 2 of 10 A variety of acylsilanes have been synthesized up to date using different methods, the reactions of protected aldehydes, esters, and other carboxylic acid derivatives, etc. with various silicon reagents [1–9]. During the course of our studies of the reactions of an isolable dialkylsilylene with various functional groups [26–30], we have found that the silylene inserts exclusively into the C–Cl bond Molecules 2016, 21, 1376 2 of 9 of aroyl chlorides providing rather exceptional aroyl(chloro)silanes that cannot be obtained via aroylMoleculesconventional chlorides 2016, 21, methods.1376 providing Very rather recently, exceptional an acyl(halo)silane aroyl(chloro)silanes was utilized that cannot to synthesize be obtained an isolable 2 viaof 9 conventionalsilenyllithium methods. (Equation Very (3)) [recently,31]. an acyl(halo)silane was utilized to synthesize an isolable silenyllithiumaroyl chlorides (Equ providingation (3)) rather[31]. exceptional aroyl(chloro)silanes that cannot be obtained via conventional methods. Very recently, an acyl(halo)silane was utilized to synthesize an isolable silenyllithium
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