【作者】 杨波；

【导师】 王中夏；

【作者基本信息】 中国科学技术大学 ， 有机化学， 2019， 博士

【摘要】 本论文研究了烯丙基C-O键、芳基C-S键和C-N键的活化与转化。我们分别实现了镍催化下烯丙醇的C-O键切断和三甲基铵盐的C-N键切断。同时,我们也实现了无过渡金属参与条件下芳基或者杂芳基硫酚的C-S键断裂。第1章介绍了镍催化下烯丙醇与芳基或者烯基锌试剂的交叉偶联反应。Ni(OTf)2/dppe可以有效地催化各种烯丙醇与芳基或者烯基锌试剂的反应,实现碳-氧键的切断和碳-碳键的构建。该反应展现出了高度的区域选择性,反式-3-芳基烯丙醇和1-芳基烯丙醇的底物反应产生的都是线性目标产物。反应也具有良好的E/Z选择性,对于大部分底物得到的是双键为反式构型的产物。该催化体系也适用于二级烯丙醇,反应同样具有良好的区域选择性并得到双键五-构型产物。反应可能是经过一个Ni(0)/Ni(Ⅱ)的循环过程,锂、镁和锌离子在催化反应中具有重要作用。第2章展示了NiCl2(PMe3)2催化下烯丙醇与硅基锌试剂的交叉偶联反应。该反应条件温和,兼容多种官能团,如OMe、OPh、NMe2、CF3、OCF3、OCHF2、F、Cl、SMe、CO2Me、C(O)NEt2和含氧、氮、硫杂环。反应展现出了优秀的区域选择性,反式-3-芳基烯丙醇和1-芳基烯丙醇的底物反应产生的都是线性目标产物。此外,反应也具有良好的E/Z选择性,对于大部分底物得到的是双键为反式构型的产物。第3章研究了无过渡金属参与的芳基和杂芳基硫酚与芳基锌试剂的交叉偶联反应。反应具有宽的底物范围和良好的官能团容忍性。贫电子和富电子芳基或杂芳基硫酚都能实现转换。各种芳基锌试剂如富电子和贫电子的锌试剂都可以顺利地发生反应。初步的研究机理表明该反应是一个芳基亲核取代过程,Mg2+与Li+离子在反应中具有重要作用。第4章介绍了NiCl2(dppf)催化芳基、苄基或者烯丙基铵盐与含膦亲核试剂的交叉偶联反应。通过该反应合成了一系列铵盐的膦化产物,大多数情况下都可以得到中等至优秀的产率。这一方法具有宽的底物范围,可以容忍OMe、CN、CF3、F、Cl、C(O)NMe2和C(O)tBu等官能团。反应可能是经过一个Ni(0)/Ni(Ⅱ)的循环过程。更多还原

【Abstract】 This thesis focuses on activation and transformation of allylic C-O bonds and ar?omatic C-S and C-N bonds.We carried out the C-O bond cleavage of allyl alcohols and the C-N bond cleavage of trimethylammonium salts in the presence of nickel catalysis.We also performed the C-S bond cleavage of aryl and heteroaryl thiols under transition-metal-free conditions.Chapter 1 introduces nickel-catalyzed cross-coupling of allyl alcohols with aryl-or alkenylzinc reagents.Ni(OTf)2/dppe was demonstrated to effectively catalyze the reaction,resulting in cleavage of the C-O bonds and formation of C-C bonds.The re?action exhibits high regioselectivity.Reaction of both(E)-3-arylprop-2-en-l-ols and 1-aryl-prop-2-en-l-ols substrates results in linear coupling products.The reaction also shows good EiZ selectivity for the new C-C double bonds,(E)-geometry alkenes being formed in most cases.The catalyst system is also suited for the coupling of secondary allyl alcohols to afford regioselective coupling products with(E)-C-C double bond ge-ometry.The reaction might proceed through a Ni(0)/Ni(Ⅱ)cycle.Lithium,magnesium,and zinc ions play important roles in the catalytic process.Chapter 2 presents the synthesis of allyl silanes via NiCl2(PMe3)2-catalyzed cross-coupling of allyl alcohols with silylzinc reagents.The method performs the reactions under mild conditions and can tolerate functional groups including OMe,OPh,NMe2,CF3,OCF3,OCHF2,F,Cl,SMe,CO2Me,C(O)NEt2 groups and oxygen-,nitrogen-,sulfur-contaning heterocycles.The reaction exhibits high regioselectivity,both(E)-3-arylprop-2-en-l-ols and 1-aryl-prop-2-en-l-ols resulting in linear coupling products.The reaction also shows good E/Z selectivity for the new formed C-C double bonds,(E)-geometry alkenes being formed in most cases.Chapter 3 describs transition-metal-free cross-coupling of aryl and heteroaryl thi-ols with arylzinc reagents.The reaction exhibited wide substrate scope and good com-patibility of functional groups.Electron-rich and-poor aryl or heteroaryl thiols can be converted.Various arylzinc reagents,including electron-rich and electron-poor reagents,can be employed as the coupling partners.Preliminary mechanistic studies suggest a nucleophilic aromatic substitution pathway,and Mg2+ and Li+ ions play important roles in the process of reaction.Chapter 4 reveals NiCl2(dppf)-catalyzed C-P coupling of aryl,benzyl,or allyl am-monium salts with P(O)H compounds.Through the reaction a series of phosphonylation products of the ammonium salts were synthesized in reasonable to excellent yields in most cases.The method accomodates a wide scope of substrates and tolerates a range of functional groups such as OMe,CN,CF3,F,Cl,C(O)NMe2,and C(O)tBu.The reaction might proceed through a Ni(O)/Ni(Ⅱ)cycle process.更多还原