【作者】 徐鲁斌；

【导师】 黄宪；

【作者基本信息】 浙江大学 ， 有机化学， 2006， 博士

【摘要】 本文主要研究了1，3-二羰基化合物与联烯溴在碱性条件下的加成—环合串联反应，一氯二茂钛诱导的环氧联烯的分子内自由基环化反应及炔基氧膦的硅铜化反应。全文共分三个部分：一、研究了在碱性条件下1，3-二羰基化合物与联烯溴的反应。（1）在以氢化钠作碱的条件下，丙二酸二甲酯与单（双）芳基取代的联烯溴发生亲核加成—分子内亲核取代成环的串联反应，最终生成芳基亚甲基环丙烷-1，1-二羧酸酯类化合物；而与烷基取代的联烯溴反应则发生S_N2’型反应，最终生成炔基酯类化合物。（2）在以K₂CO₃作碱的条件下，1，3-二酮与单芳基取代的联烯溴发生亲核加成—亲核取代成化的串联反应，最终生成了2，3，4-三取代呋哺类化合物。上述结果是有关联烯溴作为烯丙基双正离子等当体的首例报道，反应结果证实了我们所设想的反应历程是可行的。二、我们将环氧与联烯结构单元构建在同一分子内，研究了Cp₂TiCl诱导的自由基环化反应。结果发现，该反应高区域选择性的以5-exo方式进行环合，得到了一类合成上非常有用的3-烯基—4—羟甲基四氢呋喃类化合物，提供了一条合成该类化合物的新方法，该方法与文献相比具有简介、有效等特点。同时该反应还可拓展到合成多官能化的五元碳环（或氮杂环）。三、研究了有机硅铜试剂与炔基氧膦的硅铜化反应，反应可有效在β位引入有机硅基团，同时生成的二苯基氧膦烯基铜中间体，可以被多种亲电试剂如I₂，PhSeBr，PhTeI，烯丙基溴等捕获，合成了β—有机硅基—α—官能化的烯基二苯基氧膦和多取代的1，4—二烯。这为多官能化烯基二苯基氧膦的立体及区域选择性的合成提供了一条新的途径。更多还原

【Abstract】 In this dissertation, the tandem reactions of bromoallenes with 1, 3-dicarbonyl compounds in the presence of a base; the Cp2TiCl-mediated intramolecular radiacl cyclization of epoxy-allenes; and the silylcupration of alkynylphosphine oxides were investigated.Firstly, the tandem addition-cyclization of bromoallenes with 1, 3-dicarbonyl compounds was investigated. （1） the tandem addition-cyclization of dimethyl malonate with mono- or diarylsubstituted bromoallenes in the presence of NaH to give corresponding （E）-dimethyl arylmethylidenecyclopropane-1, 1-dicarboxylates; however, the reaction with alkylsubstituted bromoallenes proceeded in a S_n2’ manner to give acetylenic esters. （2） the tandem addition-cyclization of 1, 3-diketones with monosubstituted bromoallenes in the presence of K₂CO₃ to give corresponding 2, 3, 4-trisubstituted furans. These results are the first present of intermolecular cyclization about bromoallenes used as allyl dication equivalents.Secondly, the Cp₂TiCl-mediated radical cyclization of epoxy-allenes was investigated. The carbon radical generated from epoxide group in the presence of Cp₂TiCl attack allenyl group in a highly regioselectively 5-exo mode to cyclize and to give synthetically useful 3-vinyl-4-hydroxymethane-tetrahydrofunan compounds. The reaction provided a new and efficient method for synthesis of this kind of compounds. The method has the advantages of available materials. simple manipulation. Also this method could be extended to synthesize polyfunctional five-membered carbon or nitrogen cycles.Thirdly, silylcupration of alkynylphosphine oxides was investigated. This reaction could efficiently synthesis ofβ-silylsubstituted vinylphosphine oxides with high stereo-and regioselectivity. The key vinylcopper intermediate stabilized by the diphenylphosphine oxide react with electrophiles, such as I₂, PhSeBr. PhTeI and allyl bromide to giveβ-silyl-α-functionalized vinylphosphine oxides and 1, 4-dienes.更多还原