镧系金属催化不对称环加成反应研究进展

综述了近年来镧系金属催化不对称环加成反应的研究进展,主要包括[4+2]、[3+2]、[2+2]和[2+1]不对称环加成反应.并对部分环加成反应可能的机理进行了讨论.     

铜酞菁的溶解及纳米铜酞菁薄膜的制备

通过增加铜酞菁（CuPc）溶液中三氟乙酸（TFA）的浓度,使铜酞菁发生质子化反应得到[CuPc·H]^＋和[CuPc·H2]^2＋两种衍生物,并用紫外可见分光光度计进行表征．[CuPc·H]^＋和[CuPc·H2]^2＋两种衍生物的Q带相继发生红移．[CuPc·H]^＋和[CuPc·H2]^2＋两种衍生物的Q带都发生裂分,表明两种衍生物具有不对称结构．铜酞菁发生质子化反应后在有机溶剂中的溶解度增大了60倍,放置两周后不会发生降解．以发生质子化反应的铜酞菁溶液为电解液,用电沉积方法在ITO导电玻璃上制备铜酞菁薄膜,并用扫描电镜（SEM）和X射线衍射（XRD）进行表征．在ITO基片上沉积的纳米CuPc薄膜,尺寸在100—200nm之间,具有口相晶体结构,分子的堆积方向（b轴）平行于基片．     

手性Salen-Co(Ⅱ)配合物催化芳香酮不对称还原反应研究

目前 ,以廉价的氢气为氢源 ,由潜手性的酮不对称加氢是制备手性醇最好的方法之一 [1] .但存在手性催化剂的膦配体不稳定以及贵金属 ( Ru、Rh)的流失等问题 .硼氢化钠是一种较温和的氢化试剂 ,Mukaiyama等用具有 C2 对称轴的一系列光学活性的二亚胺钴配合物催化硼氢化钠不对称还原芳香酮 ,实现了以硼氢化钠为氢源的不对称氢化反应 [2 ] .手性 Salen是一种用途广泛的配体 ,已用在不对称催化环氧化 [3 ]、环丙烷化 [4]、杂 Diels- Alder反应 [5]及环氧化合物的水解动力学拆分 [6]、仲醇动力学拆分[7] 等反应中 ,并显示出很好的不对称诱导效…     

新的手性联吡啶配体立体选择催化环丙烷化

近年来,手性联吡啶已广泛应用于不对称均相催化,如不对称环丙烷化[1]、烯丙位氧化[1]、烯丙位取代[2]及有机锌加成醛[3]等反应.     

合成文拉法星的2-氮杂-1,3-丁二烯杂Diels-Alder反应与其 单分子环合竞争反应的研究

研究了不同的Lewis酸催化剂、温度、微波等条件下, 4-(4-甲氧苯基)-1-苯基-3-三甲基硅氧基-2-氮杂-1,3-丁二烯(2-ABDE)和亲二烯体环己酮发生杂Diels-Alder反应生成[4＋2]的六元环合产物噁嗪酮衍生物, 伴随的2-ABDE的 [2＋2]单分子环合, 生成单环β-内酰胺衍生物. 结果表明: 在低温条件下如(－78 ℃)[4＋2]反应占主导; 而在高温条件下(如135 ℃)仅进行[2＋2]反应. 微波加热方式可显著提高[2＋2]反应的速率和产率. 不同的Lewis酸催化剂对[2＋2]反应和[4＋2]反应的催化效率不同. Lewis酸的酸性强弱、软硬对2-ABDE的[2＋2]反应的催化能力起决定性作用.     

苄连氮基桥联的双杯[4]芳烃的合成

对叔丁基杯[4]芳烃-1, 3-二醛基衍生物1分别与水杨醛腙、水合肼进行“1＋2”和“2＋2”缩合反应, 方便地合成了苄连氮基取代或桥联的新型杯[4]芳烃衍生物2和双杯[4]芳烃衍生物3, 产率分别为84%和81%. 新化合物的结构与构象经元素分析、质谱、核磁共振谱和1H-1H COSY谱图等表征证实, 双杯[4]芳烃衍生物3为空间结构完全对称的具有管状三维空腔的杯式构象.     

一类新的红色荧光粉MYzS4：Er^3＋（M=Srz＋，Ba^2＋）的合成与表征

Eu^2＋激活的CaS：Eu^[1],Eu^3＋和Sm^3＋激活的硫氧化物^[2]，Pr^3＋激活的Ca0.8Zn0.2Ti03^[3]以及Eu^2＋和Mn^2＋掺杂的SrY2S4^[4]都是重要的红色发光材料。然而，这些红色荧光粉的发射峰波长都短于650nm，对于农用日光转换材料^[5]，红色发射峰波长达到660nm才能与叶绿素的红区吸收相吻合。     

La3+,Sr2+置换对Ca[(Mg1/3Nb2/3)0.6Ti0.4]O3陶瓷微波介电性能的影响

研究了La^3＋，Sr^2＋置换对Ca[（Mg1/3Nb2/3）0.6Ti0.4]O3陶瓷微观结构与微波介电性能的影响。研究结果表明：La^3＋，Sr^2＋置换改性Ca[（Mg1/3Nb2/3）0.6Ti0.4]O3系列陶瓷均形成了单一正交系的钙钛矿结构；随着置换量的增加，La^3＋改性Ca[（Mg1/3Nb2/3）0.6Ti0.4]O3陶瓷的介电常数、介电损耗下降，同时谐振频率温度系数向正的方向移动，而Sr^2＋改性陶瓷则表现出相反的规律，其主要原因在于La^3＋，Sr^2＋置换所引起Ca[（Mg1/3Nb2/3）0.6TiO4]O3陶瓷内部氧八面体结构变化上的差异。     

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.     

树脂固定化手性联萘酚-钛催化剂的合成及其催化特性研究

自从Ｍｅｒｒｉｆｉｅｌｅｄ首创多肽的固相合成以来 ,以聚苯乙烯树脂为支持物的合成方法在化学及生物化学等领域得到广范应用[1～ 3] .作为该方法的一个新的发展方向 ,将手性配体联接在多聚物上用于非均相不对称催化已成为当前不对称合成的热门领域之一 .近年来踊现出大量多聚物固定化的手性不对称催化剂 ,在二乙基锌对醛的不对称加成[4] 及Ｄｉｅｌｓ Ａｌｄｅｒ等[5] 反应中显示出优良的不对称催化能力 .光学活性的 1 ,1’ 联萘 2 酚 (ＢＩＮＯＬ)是不对称催化中应用最广泛的配体之一[6～ 9] .为了将ＢＩＮＯＬ引入非均相不对称催化 ,我…     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.     

Copper-catalyzed multicomponent reactions of 2-iodoanilines,benzylamines, and elemental sulfur toward 2-arylbenzothiazoles

A relatively cheap copper salt-catalyzed, three-component approach providing 2-arylbenzothiazoles in good to excellent yields from readily available 2-iodoanilines, benzylamines, and sulfur powder is reported. This methodology allows preparation of various classes of 2-arylbenzothiazoles and provides a general, reliable approach.