【作者】 李晶；

【导师】 傅春玲； 麻生明；

【作者基本信息】 浙江大学 ， 有机化学， 2009， 博士

【摘要】 本论文主要研究了2,3-联烯醇的合成及其与卤素的亲电性1,2-迁移反应,主要包括以下三部分内容：第一部分：2,3-联烯醇与卤素的亲电性1,2-迁移反应研究首先,我们研究了2,3-联烯仲醇与卤素的亲电性1,2-迁移反应,发现羟基α-位取代基性质对反应选择性有显著影响：当取代基为芳基时,主要发生1,2-芳基迁移生成β-卤代-β,γ-不饱和烯醛；当取代基为甲基时,主要发生1,2-氢迁移生成β-卤代-β,γ-不饱和烯酮。接着,我们又研究了2,3-联烯叔醇与NBS的亲电性1,2-迁移反应,发现溶剂效应对反应选择性有着较大的影响,以水为溶剂时反应区域选择性地生成β-溴代-β,γ-不饱和烯酮。当羟基α-位两个取代基均为烷基时,发生1,2-烷基迁移,其中1-丙二烯基环醇为底物时可发生扩环反应生成α-(1’-溴)乙烯基环酮；当羟基α-位至少有一个取代基为芳基时发生1,2-芳基迁移。在上述研究基础上,我们发展了由2,3-联烯叔醇一步制备1,2-联烯酮的方法。第二部分：光学活性2,3-联烯醇的制备为了研究光学活性联烯醇的合成,我们发展了溴化亚铜催化下由末端炔一锅法制备简单联烯的方法,并在此基础上发展了由外消旋炔丙醇出发分步合成光学活性2,3-联烯仲醇的方法,产物ee值最高为99.7%。但反应产率偏低,且只能合成1-位取代基为芳基的光学活性2,3-联烯仲醇。因此,我们对上述方法做了改进,发展了氰化亚铜催化的由光学活性的4-氯-2-丁炔醇化合物与烷基格氏试剂作用制备光学活性的2,3-联烯仲醇的方法,反应产率良好到优秀,ee值最高为99.9%,解决了上述溴化亚铜催化下制备光学活性2,3-联烯仲醇反应产率较低和产物取代基局限性较大的不足之处。当芳基格氏试剂替换烷基格氏试剂与4-氯-2-丁炔醇类化合物反应时,产物为2-炔醇化合物而非2,3-联烯仲醇。第三部分：光学活性2,3-联烯醇与溴的亲电性1,2-迁移反应研究在上一部分中,我们成功制备了高ee值的光学活性2,3-联烯醇,于是我们对光学活性2,3-联烯仲醇与溴的亲电性1,2-迁移反应进行了研究,反应区域选择性得到光学活性β-溴代-β,γ-不饱和烯醛产物,该反应中联烯醇的碳中心手性只有部分转移至产物中的中心手性,产物ee值最高为76.0%。更多还原

【Abstract】 In this dissertation, much attention has been focused on the synthesis of 2,3-allenols and its electrophilic 1,2-shift reactions with X+. The whole dissertation can be divided into three parts:PartⅠ:Electrophilic 1,2-shift reactions of 2,3-allenols with electrophilic halogen atom reagentsFirstly, we studied the electrophilic 1,2-shift reactions of secondary 2,3-allenols with X+. It was found that different substitutent groups have different tendancy for 1,2-shift:When there is an aryl group at the a-position, the reaction affordedβ-halo-β,γ-alkenals via a 1,2-aryl shift; when there is a methyl group on the a-position, the reaction affordedβ-halo-β,γ-alkenones via a 1,2-H shift.Secondly, we studied the electrophilic 1,2-shift reactions of tertiary 2,3-allenols with NBS. It was found that solvent effect have a great impact on the reaction selectivity. Water was found to be the best solvent, which affordedβ-bromo-β,γ-alkenones with high regioselectivity. When the a-substitutent groups are both alkyl groups, the reaction proceeded via a 1,2-alkyl shift; with cyclic allenols, a ring expansion was observed to affordα-(1’-bromo)vinylcyclic ketones. When there’s at least one aryl group at theα-position, the reaction proceeded via a 1,2-aryl shift. Based on the above results, we have also developed an effective method for the synthesis of 1,2-allenic ketones from tertiary 2,3-allenols.PartⅡ:Preparation of optically active 2,3-allenolsWe have developed an effective methodology for the CuBr-catalyzed one-pot synthesis of simple allenes from terminal alkynes. Based on this work, we synthesized optically active secondary 2,3-allenols from racemic propargyl alcohols with up to 99.7% ee value in three steps.However, the yield is not satisfactory and only optically active 1-aryl-2,3-allenols can be prepared.In order to solve these problems, we developed the CuCN-catalyzed carbometallation of optically active 4-chloro-2-butynols with alkyl Grignard reagent, which afforded optically active secondary 2,3-allenols with good yield and up to 99.9% ee value. Compared with the above CuBr-catalyzed synthesis of 2,3-allenols, the yield is satisfactory and the 1-substituent group can be aryl or alkyl group. When aryl Grignard reagents reacted with 4-chloro-2-butynols, the reaction afforded propargyl alcohols instead of 2,3-allenols.PartⅢ:Electrophilic 1,2-shift reactions of optically active 2,3-allenols with bromineAfter being successful in the synthesis of optically active 2,3-allenols with high ee value, we studied the electrophilic reaction of optically active 2,3-allenols with bromine and demonstrated that this reaction afforded optically activeβ-bromo-β,γ-alkenals with high regioselectivity. The chirality of the optically active 2,3-allenols can be partly transferred into the center chirality in the final products with up to 76.0% ee value.更多还原