[60]富勒烯[2＋2]环加成反应的研究进展

[2＋2]环加成反应是对C₆₀进行化学修饰的重要反应之一, 重点从[2＋2]环加成的典型反应、主要试剂及反应机理等方面进行了综述.     

钯催化[4+2]环加成反应的研究进展

综述了近年来钯催化[4+2]环加成反应的研究进展.重点讨论了钯催化[4+2]环加成反应的影响因素,如二烯体和亲二烯体、催化剂用量、配体、溶剂、反离子、温度及反应时间     

[60]富勒烯[2＋3]环加成反应的研究进展

对[60]富勒烯[2＋3]环加成反应的研究进展进行了综述，并介绍了在环加成反应中使用的主要试剂及反应机理.     

催化不对称[8+2]环加成反应构建环庚三烯并吡咯烷-3,3'-吲哚酮

设计了azaheptafulvenes作为偶极子与N-Boc-3-烯基吲哚酮反应,用来构建螺环[吡咯烷-3,3'-吲哚酮]衍生物.在1mol%手性氮氧-Ni(II)配合物催化剂条件下,该不对称[8+2]环加成反应以高的收率(90%~99%收率),好的非对映选择性(高达97∶3 dr)和优异的对映选择性(92%~99%ee)得到手性环庚三烯并螺环[吡咯烷-3,3'-吲哚酮]衍生物.     

亚甲胺叶立德参与的[3＋2]环加成反应的最新进展

综述了亚甲胺叶立德的制备、它参与的[3＋2]环加成反应的反应机理、反应选择性及在天然产物全合成中的应用等方面的最新进展.     

α,β—不饱和硫酮体系[4＋2]环加成反应的研究

系统研究了β,β-不饱和硫酮在[4+2]环加成反应中的行为.选取5-芳亚甲基四氢噻唑-2,4-二硫酮作为反应的杂共轭双烯体系,与N-苯基马来酰亚胺等嗜双烯作用,得到12个新化合物.观察到丙烯酸乙酯和丙烯腈在对杂共轭双烯进行[4+2]环加成反应时存在着某种区域选择性.初步探讨了这类环加成反应条件及反应物的反应活性.     

铑催化环加成反应的研究进展

综述了近几年铑催化剂在环加成反应中的研究进展, 主要包括[2＋2], [2＋2＋1], [2＋2＋2], [3＋2], [3＋4]和[4＋2]环加成反应等, 讨论了铑催化下的环加成反应及其机理.     

过渡金属催化[2+2+2]环加成反应合成吡啶衍生物

环加成反应可以一步同时构建多个化学键,是目前国内外研究最为活跃的领域之一。相比于传统方法,过渡金属催化的[2+2+2]环加成反应是合成吡啶衍生物的有效手段。本文从反应机理、非手性吡啶化合物合成和手性吡啶化合物合成三个方面阐述了近年来吡啶衍生物的研究情况,涉及Co、Rh、Ru、Fe、Ni、Ti等金属催化体系。     

含吡唑基查尔酮的[2+2]环加成反应研究

在氢氧化钾存在下,用4-甲酰基吡唑类化合物和取代苯乙酮发生反应得到含吡唑基查尔酮的[2+2]环加成产物,对其进行了波谱表征,并对其反应机理进行了讨论.     

[4+3]环加成反应研究进展

本文对[4+ 3 ]环加成反应体系以及最近在合成中的应用进行了综述, 并对进一步研究的方向进行了讨论。     

Catalyst-Free [3+2] Cycloaddition of Isoquinolinium/Pyridinium Ylides and Electron-Deficient Alkenes

The development of simple-to-operate methods for the preparation of indolizidine derivatives are of great importance. A mild one-pot protocol for the [3+2] cycloaddition of isoquinolinium/pyridinium ylides and electron-deficient alkenes using NaBH₃CN as reductant has been developed. The protocol has a broad substrate scope (more than 40 examples) and provides various novel hexahydroindolizidine derivatives in high yields and excellent diastereoselectivities (up to >20/1).     

有机催化不对称[4+2]环加成反应*

有机催化不对称合成反应是目前国内外研究最为活跃的领域之一。不对称[4+2]环加成（Diels-Alder）反应是合成光学活性环状化合物的有效手段,目前报道的催化不对称Diels-Alder反应的有机催化剂主要有手性咪唑啉酮、手性Br?nsted酸、手性伯胺、金鸡纳碱衍生物等。本文对各类有机催化剂在有机催化不对称Diels-Alder反应中的应用研究进展,以及不对称诱导反应的机理进行了评述。     

Predicting Dinitrogen Activation via Transition-Metal-Involved [4+2] Cycloaddition Reaction

As the strongest triple bond in nature, the N≡N triple bond activation has always been a challenging project in chemistry. On the other hand, since the award of the Nobel Prize in Chemistry in 1950, the Diels-Alder reaction has served as a powerful and widely applied tool in the synthesis of natural products and new materials. However, the application of the Diels-Alder reaction to dinitrogen activation remains less developed. Here we first demonstrate that a transition-metal-involved [4+2] Diels-Alder cycloaddition reaction could be used to activate dinitrogen without an additional reductant by density functional theory calculations. Further study reveals that such a dinitrogen activation by 1-metalla-1,3-dienes screened out from a series of transition metal complexes (38 species) according to the effects of metal center, ligand, and substituents can become favorable both thermodynamically (with an exergonicity of 28.2 kcal mol⁻¹) and kinetically (with an activation energy as low as 13.8 kcal mol⁻¹). Our findings highlight an important application of the Diels-Alder reaction in dinitrogen activation, inviting experimental chemists’ verification.     

氮杂环卡宾催化烯酮与氰基查尔酮的[4+2]不对称环加成反应

报道了氮杂环卡宾催化烯酮与氰基查尔酮的[4+2]不对称环加成反应. 通过L-焦谷氨酸衍生的大位阻卡宾催化烯酮与氰基查尔酮反应,以良好的产率、良好的顺反选择性和优良的对映选择性得到相应的手性多取代二氢吡喃酮类化合物.     

Thermally-Induced Intramolecular [4+2] Cycloaddition of Allylamino- or Allyloxy-Tethered Alkylidenecyclopropanes

A thermally-induced intramolecular [4+2] cycloaddition reaction of allylamino- or allyloxy-tethered alkylidenecyclopropanes has been reported in this paper, giving a new protocol for the rapid construction of polycyclic skeleton molecules in moderate to excellent yields with a broad substrate scope. On the basis of control experiments and DFT calculations, we disclosed that the reaction proceeded through a [4+2] cycloaddition and trace of water assisted 1,3-H shift process to give the target product.