Abstract
The reactions of L [PhC(NtBu)2SiCl] and L′ [CH{(C═CH2)(CMe)(2,6-iPr2C6H3N)2}Si] with monoketones and quinone have been examined. The reaction of L with 2-adamantanone furnishes a [1 + 2]–cycloaddition product 1, whereas with 3,5-di-tert-butyl-o-benzoquinone leads to the [1 + 4]–cycloaddition product 2. The treatment of L′ with 3,5-di-tert-butyl-o-benzoquinone gives [1 + 4]–cycloaddition product 3, and the reaction with acylferrocene yields compound 4. Compounds 1–4 were characterized by single crystal X-ray structural analysis, NMR spectroscopy, EI–MS spectrometry, and elemental analysis.
Highlights
Silylenes are silicon analogues of carbenes and exist with neutral divalent silicon atoms.[1]
The reactivity pattern of N-heterocyclic silylene (NHSi) is quite comparable with that of the N-heterocyclic carbenes (NHCs), where the latter led to many applications in chemistry.[5,6]
The reactions of silylenes with organic substrates lead to a number of interesting new organosilicon compounds, which are otherwise difficult to achieve.1e,f Recently, we became interested in the reactivity studies of silylenes L [NP)h2C}S(iN] tBtouw)a2SrdiCol]rgaanndicL0s[uCbsHtr{a(teCs.d3bC,9bHÀ29)d(,1C3,1M9 eI)n(s2p,6ir-eiPdr2bCy6Hth3ediverse reactivity shown by silylenes with ketones,8a,9d,16a,19a,19d we report the reactions of silylenes L and L0 with 2-adamantanone, 3,5-di-tert-butyl-o-benzoquinone, and acylferrocene
Summary
Silylenes are silicon analogues of carbenes and exist with neutral divalent silicon atoms.[1]. Many stable NHSis1bÀd,[3] and other silylenes have been isolated.[4] The reactivity pattern of NHSis is quite comparable with that of the N-heterocyclic carbenes (NHCs), where the latter led to many applications in chemistry.[5,6] Silylenes have two nonbonding electrons in the HOMO which possess nucleophilic character, and an empty 3p-orbital as the LUMO which causes electrophilic properties They possess both nucleophilic and electrophilic reactive sites at the same silicon atom, they are ambiphilic and behave as Lewis acids as well as Lewis bases.[7] Owing to this, there is an extensive research activity going on in the chemistry of NHSis, which is very challenging (insertion: CÀH,[8] NÀH,[9] OÀH,[10] SÀH,9a PÀP,[11] NÀSi,[12] CÀF,[13] CÀX (Cl, Br, I),[14] SiÀCl,[14] PÀH,[15] AsÀH,[15] addition,8a,9c,9d,16 metal complexes,[17] Lewis acids[18]). Treatment of L0 with 3,5-di-tertbutyl-o-benzoquinone affords the [1 + 4]Àcycloaddition product 3, and the reaction with acylferrocene gives compound 4
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