1,1′-联萘-2,2′-二胺的合成及在不对称合成中的应用

综述了 1,1′ 联萘 2 ,2′ 二胺 (联萘胺 )化合物的制备 ,讨论了它们作为手性辅助基或配体在烯烃、酮、亚胺的不对称氢化及在烯烃的不对称环丙烷化、醛的烷基化反应、醛的不对称烯丙基化反应、不对称烯丙位取代反应和不对称Diels Alder反应等反应中的应用 .     

手性环状二胺催化的不对称Diels-Alder反应

研究了一种结构新颖、合成路线简单的手性二胺催化的Diels-Alder反应,考察了各种Br nsted酸助催化剂、温度、溶剂和手性二胺分子中不同的取代基对反应的影响.研究结果表明:该类催化剂在催化Diels-Alder反应中表现出较高的催化活性和中等的立体选择性.     

1，1′－联萘－2，2′－二胺的合成及在不对称合成中的应用

综述了1，1′－联萘－2，2′－二胺（联萘胺）化合物的制备，讨论了它们作 为手性辅助基或配体在烯烃、酮、亚胺的不对称氢化及在烯烃的不对称环丙烷化、 醛的烷基化反应、醛的不对称烯丙基化反应、不对称烯丙位取代反应和不对称 Diels-Alder反应等反应中的应用。     

手性联萘胺衍生物为配体的铜络合物催化下某些烯烃的不对称环丙烷化反应

以1,1'-联萘-2,2'-二胺为手性源合成了8对16种光活性铜络合物,考察了它们对1,1-二苯乙烯、苯乙烯和2,5-二甲基-2,4-己二烯等3种烯烃的不对称环丙烷化反应的光学诱导活性.结果表明,以旋光活性联萘胺同水杨醛及2-羟基萘甲醛缩合而得到的Schiff碱为配体的铜络合物的催化效果最佳.催化剂对2,5-二甲基-2,4-己二烯的催化效果优于其它两种烯烃.     

铜化合物催化重氮乙酸乙酯环丙烷化反应

研究了以铜化合物催化重氮乙酸乙酯与烯烃的环丙烷化反应,首次计算了反应关键中间体铜-卡宾的环丙烷化选择性P及该中间体的解离常数K,结果表明:1.反应体系中可能存在着铜-卡宾与游离卡宾的平衡;2.P、K与所用的催化剂有关。使用不同的催化剂,温度对反应选择性的影响也不同,对以上结果进行了理论探讨。     

手性联萘胺衍生物为配体的铜络合物催化下某些烯烃的不对…

以１，１＇－联萘－２，２＇－二胺为手性源合成了８对１６种光活性铜络合物，考察了它们对１，１－二苯乙烯、苯乙烯和２，５－二甲基－２，４－己二烯等３种烯烃的不对称环丙烷化反应的光学诱导活，，诱旋光活性联萘胺同水杨醛及２－羟基萘甲醛缩合而得到的ｃｈｉｆｆ碱为配体的铜络合物的催化效果最佳，催化剂对２，５－二甲基－２，４－己二烯的催化效果优于其它两种烯烃。     

不同直链二胺对敏化石墨烯制氢光催化剂性能的影响

采用一步水热法合成方法,分别利用乙二胺(1,2-EDA),1,3-丙二胺(1,3-PDA), 1,4-丁二胺(1,4-BDA)和1,5-二胺基戊烷(1,5-PDA) 4种不同碳链长度的直链二胺与氧化石墨烯(GO)进行胺缩合反应(ACR),在GO表面构筑了链接基团,再利用这些经过化学修饰的GO为载体,构筑了染料敏化的光催化剂,研究了它们在可见光辐照下的产氢性能.结果表明,用乙二胺经ACR反应处理的GO呈现出皱褶结构,所制备的催化剂较未处理催化剂的产氢活性高出1.9倍,反应2 h产生1308.6μmol的氢气,而用其它二胺处理过的GO活性并没有明显变化.多种表征方法的结果表明,乙二胺通过ACR反应在GO上形成了具有共轭特性的皱褶官能团,这些官能团缩短了在GO表面电荷传输路径,提高了催化剂的电荷传导能力,催化剂表现出更高的电导率、更长的激子寿命,制氢催化活性也更高.相反,其它二胺不能形成具有共轭特性的官能团,因此催化活性变化不明显,甚至还有降低.结果表明,在GO上修饰适当的官能团是一种构筑高效太阳能光催化制氢催化剂的新策略.     

链接基团对固载手性Salen Mn(m)催化不对称环氧化反应的影响

制备了二胺和二酚修饰的晶态有机聚合物-无机杂化载体低聚苯乙烯基膦酸-膦酸氢锆(LCZSPP)轴向固载手性Salen Mn(Ⅲ)催化剂,将其应用于非官能烯烃的多相不对称环氧化反应.研究了两类轴向连接基团及助催化剂在催化不对称环氧化反应中的影响.结果表明,通过二胺为链接基团固载的催化剂在加入轴向助剂(NMO)的情况下,转化...     

吡咯烷酮衍生物的直接胺化:构建偕二胺衍生物

研究了对甲苯磺酸(PTSA)催化的吡咯烷酮化合物与各种N-亲核试剂的胺化反应.该方法通过简单抽滤就能以中等至优良产率得到一系列的偕二胺化合物,后处理简单无需柱层析,且可以将反应放大至克级规模.     

一个新的Cu(II)-二胺配合物催化的Henry反应

研究了L-脯氨酸制得的C2-对称二胺,与醋酸铜形成新的配合物,催化各种醛与硝基烷烃间的Henry反应。 考察了反应温度、溶剂和催化剂用量对收率和反应速率的影响。 研究结果表明,在室温下,以乙醇作为反应溶剂时,摩尔分数10%的二胺醋酸铜配合物能够有效地催化醛与硝基甲烷反应,生成相应的β-硝基醇,收率为60%~92%。 醛与硝基乙烷的Henry反应产物具有非对映立体选择性。 芳香醛参与Henry反应产物的非对映选择性高达24∶1,但脂肪醛为底物时,此催化剂对Henry反应的非对映选择性不明显。     

Organocatalyzed regio- and stereoselective diamination of functionalized alkenes

The first organocatalyzed diamination reaction of alkenes with N,N-dichlorotoluenesulfonamide (TsNCl₂) and acetonitrile as nitrogen sources was reported. The catalytic diamination reaction was convenient to carry out, resulting in imidazoline products with good yields and excellent regio- and stereoselectivities. Several other organic molecules were also tried as catalyst for this reaction and good results were achieved. A new one-pot synthesis of vicinal diamines via the current PPh₃-catalyzed diamination and the hydrolysis of resulting imidazoline products with SnCl₄ as promoter was also established.     

Copper-catalyzed diamination of unactivated alkenes with hydroxylamines

A copper-catalyzed regio- and stereoselective diamination of unactivated alkenes has been developed with O-acylhydroxylamines as electrophilic nitrogen sources and oxidants. This method provides the first example of metal-catalyzed alkene diamination for directly installing an electron-rich amino group and extends the diamination scope for the synthesis of diverse 1,2-diamines. It offers a rapid and efficient approach to construct a wide range of 1,2-diamines that are an important structural motif in organic synthesis, medicines, catalysts and ligands.     

Oxidative Interception of the Hydroamination Pathway: A Gold‐Catalyzed Diamination of Alkenes

A complimentary diamination of alkenes by using homogeneous gold catalysts is described. The reaction is one of very few examples of homogeneous gold oxidation catalysis and proceeds with high selectivity under mild conditions. Individual steps of the suggested catalytic cycle were investigated on isolated model gold complexes, and new pathways for gold‐catalyzed amination reactions were established. The key step is an intramolecular alkyl–nitrogen bond formation from a gold(III) intermediate. This process validates the concept of reductive elimination from high oxidation catalyst states for this type of C? N bond forming reactions.     

Intramolecular Diamination of Alkenes with Palladium(II)/Copper(II) Bromide and IPy2BF4: The Role of Halogenated Intermediates

The oxidative intramolecular diamination of alkenes with tethered ureas and related groups as the nitrogen source has been investigated both with the iodonium reagent IPy₂BF₄ (Py=pyridine) and under palladium catalysis in the presence of copper(II) bromide as a reoxidant. For terminal alkenes, the two procedures enable selective and high‐yielding transformations. Studies with deuterated material led to the conclusion that the reactions proceed through different stereochemical pathways. An advanced protocol for palladium‐catalyzed diamination through six‐membered‐ring annulation was also developed, and the first examples of the intramolecular diamination of internal alkenes are described. In this case, the same stereochemical outcome was observed for the iodonium‐promoted and palladium‐catalyzed transformations. On this basis, it was possible to determine the importance of aminohalogenated intermediates in both diamination reactions. Overall, the disclosed procedures broaden significantly the synthetic applicability of the oxidative intramolecular diamination of alkenes.     

Palladium-catalyzed vicinal difunctionalization of internal alkenes: diastereoselective synthesis of diamines

Internal affairs: the first general palladium-catalyzed intermolecular diamination of internal alkenes employs different nitrogen sources, which add to the alkene in a regio- and diastereoselective fashion. The resulting diamination products can be converted directly into a known ligand motif.     

Electrochemistry Enabling Stereoselective Diamination of Alkenes

To achieve the stereoselective and regioselective diamination of alkenes,Xu et al.developed an electrochemical protocol for the diamination of aryl alkenes with sulfamides by using triarylamine as a redox mediator.The chemistry proceeded in an undivided cell under constant current conditions,featuring not only wide scope of substrates and reasonable yields,but also excellent diastereoselectivity(>20:1 dr)and regioselectivity.This work has been published in the Nature Communications and can be reached at https://doi.org/10.1038/s41467-019-13024-5.     

Preparation of isoindolinones via a palladium-catalyzed diamination

A Pd(II)-catalyzed cyclization using oxidative olefin diamination was developed for the preparation of isoindolinones from ortho-olefinic N-methoxybenzamides. Using the optimized reaction conditions, the desired products were obtained in up to 90% yield using NFSI as the oxidant. This reaction provides an efficient and direct access to isoindolinones with amine functionality, an important drug skeleton.     

Evolution of copper(II) as a new alkene amination promoter and catalyst

Copper(II) carboxylates and chiral copper(II) triflate·bis(oxazoline) complexes promote and catalyze intramolecular alkene carboamination, diamination and aminooxygenation reactions, creating an array of nitrogen heterocycles. High diastereoselectivity and enantioselectivity can be achieved in these transformations. This account reviews the discovery and development of these useful and interesting reactions.     

Cu(I)-catalyzed diamination of conjugated dienes. Complementary regioselectivity from two distinct mechanistic pathways involving Cu(II) and Cu(III) species

Conjugated dienes can be diaminated at the internal and/or terminal double bonds using Cu(I) as catalyst and N,N-di-t-butyldiaziridinone (1) as nitrogen source. The regioselectivity is highly dependent upon the choice of Cu(I) catalyst and the substituents on diene substrates. The diamination likely proceeds via two mechanistically distinct pathways. The N-N bond of N,N-di-t-butyldiaziridinone (1) is first homolytically cleaved by the Cu(I) catalyst to form four-membered Cu(III) species A and Cu(II) radical species B, which are in rapid equilibrium. The internal diamination likely proceeds in a concerted manner via Cu(III) species A, and the terminal diamination likely involves Cu(II) radical species B. Kinetic studies have shown that the diamination is first-order in N,N-di-t-butyldiaziridinone (1), zero-order in olefin, and first-order in total Cu(I) catalyst, and the cleavage of the N-N bond of 1 by the Cu(I) catalyst is the rate-determining step. The internal diamination is favored by use of CuBr without ligand and electron-rich dienes. The terminal diamination is favored when using CuCl-L and dienes with radical-stabilizing groups.     

Oxidative diamination of alkenes with ureas as nitrogen sources: mechanistic pathways in the presence of a high oxidation state palladium catalyst

A first palladium-catalyzed intramolecular diamination of unfunctionalized terminal alkenes has recently been reported. This study investigates the details of its mechanistic course based on NMR titration, kinetic measurements competition experiments, and deuterium labeling. It concludes a two-step procedure consisting of syn-aminopalladation with an unligated palladium(II) catalyst state followed by oxidation to palladium(IV) and subsequent C-N bond formation to give the final products as cyclic diamines. Related reactions employing sulfamides give rise to aminoalkoxy-functionalization of alkenes. This process was investigated employing deuterated alkenes and found to follow an identical mechanism where stereochemistry is concerned. It exemplifies the importance of cationic palladium(IV) intermediates prior to the final reductive elimination from palladium and proves that the nucelophile for this step stems from the immediate coordination sphere of the palladium(IV) precursor. These results have important implications for the general development of alkene 1,2-difunctionalization and for the individual processes of aminopalladation and palladium-catalyzed C(alkyl)-N bond formation.