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Acenaphtho[1,2-c]phosphole P-Oxide: A Phosphole—Naphthaleneπ-Conjugated System with High Electron Mobility

机译:ena [1,2-c]磷对氧:具有高电子迁移率的磷-萘-π共轭体系

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摘要

Naphthalene-, acenaphthene-, and acenaphthylene-fusedphosphole derivatives 3-5 were successfully prepared by uti-lizing a Till-mediated cyclization161 of dialkynylated naphtha-lene (2a),171 acenaphthene (2b), and acenaphthylene (2c),respectively, as a key step (Scheme 1). Treatment of gold(I)complexes 3b,c with excess P(NMe2)3 afforded o3-P com-pounds 4b,c, which were subsequently oxidized by m-chloro-perbenzoic acid (mCPBA) to the corresponding P-oxides5 b,c. Compound 5c was alternatively prepared in 39 % yieldby dehydrogenation of the bridging ethylene moiety of 5bwith 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). The P-oxides 5a and 5b could be directly prepared from 2a and2b in 44 and 48% yield, respectively, without isolating thecorresponding o3-P intermediates. Compound 4a was ob-tained by reduction of 5a with excess HSiC13.
机译:通过分别利用Till介导的二乙炔化石脑油(2a),171 ena(2b)和(2c)的蒂尔(Till)介导的环化作用,成功制备了萘-,fused和-稠的磷脂衍生物3-5关键步骤(方案1)。用过量的P(NMe2)3处理金(I)配合物3b,c得到o3-P化合物4b,c,随后将其用间氯过苯甲酸(mCPBA)氧化为相应的P-氧化物5b, C。或者,通过用2,3-二氯-5,6-二氰基苯并醌(DDQ)对5b的桥连乙烯部分进行脱氢,以39%的收率制备化合物5c。可以分别从2a和2b直接以44%和48%的收率制备P-氧化物5a和5b,而无需分离相应的o3-P中间体。通过用过量的HSiC13还原5a获得化合物4a。

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