3-对甲氧基苯基-和3-对羟基苯基-1-氨基-3a,4,5,9b-四氢化-9b-羟基-3H-环戊烯并[a]萘-2-甲腈的合成和晶体结构

用低价钛试剂(TiCl₄-Zn)与2-氰基-3-对甲氧基苯基-3-(1-四氢萘酮-2-基)丙腈反应合成了3-对甲氧基苯基-1-氨 基-3a,4,5,9b-四氢化-9b-羟基-3H-环戊烯并[a]萘-2-甲腈和3-对羟基苯基-1-氨基-3a,4,5,9b-四氢化-9b-羟基-3H-环戊烯并[a]萘-2-甲腈, 并用X射线衍射分析确定了这两个产物的结构.     

(αE,E)-α-(甲氧亚氨基)-2-[1-(芳香醛酮肟氧基)甲基]苯乙酸甲酯的立体选择性合成及生物活性研究

使用邻甲苯基重氮盐与乙醛酸甲酯肟偶联反应高立体选择性合成出 (E)-2-(羟基亚氨基)-2-邻甲基苯乙酸甲酯,经硫酸二甲酯的甲基化反应可得到重要的中间体(E)-2-(甲氧亚氨基)-2-邻甲基苯乙酸甲酯, 再经NBS溴化后与 (E)-芳香醛酮肟进行醚化反应最终得到目标物(αE,E)-α-(甲氧亚氨基)-2-[1-(芳香醛酮肟氧基)甲基]苯乙酸甲酯, 这些化合物多数具有很好的广谱杀菌活性.     

1-[4-(二甲氨基)苯亚甲基氨基]-4-苯基硫脲的另一个手性对映体晶体结构

对-二甲氨基苯甲醛和苯基氨基硫脲缩合反应生成1-[4-(二甲氨基)苯亚甲基氨基]-4-苯基硫脲(DMB), 产物能从溶液中析出单一手性对映体晶体. 用单晶X射线衍射技术测定了它的绝对构型, 晶体属正交晶系, P2₁2₁2₁空间群, a＝0.7870(2) nm, b＝1.1560(2) nm, c＝1.6668(3) nm, V＝1.5164(5) nm³, Z＝4, D_c＝1.307 g/cm³, F(000)＝632, μ＝0.213 mm^－1, 2557个可观测点[I＞2s(I)]精修的最终残差因子: R＝0.0409, wR＝0.1061, Flack参数为0.00(9), 能够确定绝对构型. 化合物的晶体结构和大宗粉末样品的固体圆二色谱表明化合物在结晶过程中发生单一对映体的手性堆积.     

ω-苯基-(2S)-N-叔丁氧羰基氨基酸乙酯的制备

格氏试剂和N-叔丁氧羰基焦谷氨酸乙酯反应生成中间体ω-苯基-δ-氧代-(2S)-N-叔丁氧羰基氨基酸乙酯, 分别用对甲基苯磺酰肼和醋酸硼氢化钠结合的一锅法还原或Pd/C催化氢化还原中间体得到ω-苯基-(2S)-N-叔丁氧羰基氨基酸乙酯.     

1-[4-(二甲氨基)苯亚甲基氨基]-4-苯基硫脲的合成及手性晶体结构

对二甲氨基苯甲醛和苯基氨基硫脲缩合反应生成对二甲氨基苯甲醛缩氨基苯硫脲{1-[4-(dimethylamino)ben- zylidene]-4-phenylthiosemicarbazide}, 并从溶液中析出手性晶体. 元素分析、红外光谱、紫外光谱、核磁谱、质谱和X射线衍射测定其组成和结构. 晶体属正交晶系, P2₁2₁2₁空间群, a＝0.77038(14) nm, b＝1.1428(2) nm, c＝1.6726(3) nm, V＝1.4726(5) nm³, Z＝4, D_c＝1.346 g/cm³, F(000)＝632, μ＝0.219 mm^－1, 可观测点精修最终偏离因子: R＝0.0407, wR＝0.1157. 化合物的晶体结构和固态圆二色谱表明化合物在结晶过程中发生单一对映体的手性堆积.     

手性β-氨基醇催化α,β-不饱和酮的不对称环氧化反应

将以烯烃为原料通过Sharpless不对称双羟化等多步反应合成的8种手性β-氨基醇, 作为有机小分子催化剂, 用于催化α,β-不饱和酮的不对称环氧化反应．考察了影响对映选择性的催化剂结构、催化剂用量、氧化剂种类、溶剂、反应温度等因素．结果表明, 当催化剂用量为30 mol%、氧化剂为TBHP(叔丁基过氧化氢)、正己烷溶剂、在室温下、以(1S,2R)-(＋)-1,2-二苯基-2-甲氨基乙醇(3)作催化剂时, 所得环氧化物的对映体过量最高为70% ee, 产率最高为84%.     

新型手性N,N′-双支套索冠醚的合成及其应用

(S)-苯丙氨醇和原氯乙酸三乙酯作用得到的手性酰胺醇和手性噁唑啉分别与1,7-二氮-12-冠-4反应, 得到了两种手性N,N′-双支套索冠醚N,N′-二[(S)-N-(1-羟甲基-2-苯基乙基)乙酰胺-2]-1,7-二氮-12-冠-4 (1a)和N,N′-二[(S)-4-苄基-噁唑啉-2-亚甲基]-1,7-二氮-12-冠-4 (1b). 前者应用于D/L-肉碱的手性分离; 后者的铜配合物用于重氮醋酸酯对烯烃的不对称环丙烷化反应.     

L-脯氨酸对离子液体介质中的不对称Michael反应催化性能研究

研究了L-脯氨酸对离子液体介质中醛(酮)与β-硝基烯烃的不对称Michael加成反应的催化性能, 利用X射线单晶衍射对Michael产物结构进行了表征. 结果表明, 反应在遵循胺催化机理的同时, 烯胺是从Re面对β-硝基烯烃进行加成, 产物的优势结构为(1R,2S)的syn型. 脯氨酸在离子液体1-正己基-3-甲基咪唑氯盐中显示良好的催化性能, 室温反应3～5 h, 得到89%以上收率的Michael产物, 其ee值最高70%. 脯氨酸与离子液体形成的催化体系具有良好的重复使用性能, 可至少稳定地重复使用6次.     

2',4"-O-双(三甲基硅)红霉素A 9-O-(1-乙氧基-1-甲基乙基)肟的区域选择性甲基化

一锅煮合成并表征了2',4"-O-双(三甲基硅)红霉素A 9-O-(1-乙氧基-1-甲基乙基)肟, 首次在丙酮-水混合溶剂中培养出了单晶. X射线衍射表明, 其结构为四方晶系, I4空间群, 晶胞参数: a＝b＝2.9536(1) nm, c＝1.4488(1) nm, V＝12.63897(4) nm³, Z＝8, R＝0.068, wR＝0.067. 对区域选择性影响因素的研究表明: 甲基化时溶液浓度应控制0.052 mol/L和0.067 mol/L之间; 分别采用了四氢呋喃、二氯甲烷、甲基叔丁基醚、甲苯与二甲亚砜作为混合溶剂进行甲基化反应, 发现在甲苯-二甲亚砜中的效果最好, 6-OH的甲基化选择性可达到81.69%.     

9,9-二甲基-2-(4-甲氧基苯基)-4-苯基-9H-吡啶并[1,2-a]吲哚高氯酸盐的微波合成及晶体结构

利用2,3,3-三甲基-3H-吲哚高氯酸盐、1-苯基-3-(4-甲氧基苯基)-2-丙烯-1-酮与哌啶在微波辐射条件下合成了9,9-二甲基-2-(4-甲氧基苯基)-4-苯基-9H-吡啶并[1,2-a]吲哚高氯酸盐, 在甲醇中培养出单晶, 通过X射线单晶结构分析法测定分子结构和晶体结构, 晶体属于正交晶系, Pca2₁空间群, 晶胞参数为: a＝2.7923(6) nm, b＝0.92126(17) nm, c＝1.8345(4) nm, V＝4.7190(16) nm³, D_c＝1.345 g/cm³, μ＝0.201 mm^－1, F(000)＝2000, Z＝8, R₁＝0.0566, wR₂＝0.1320.     

Insertion of ethyl diazoacetate into the platinum–carbon bond of Pt(diphosphine)(halide)(aryl) complexes. X-ray structure of the Pt{(2<Emphasis Type="BoldItalic">S</Emphasis>,4<Emphasis Type="BoldItalic">S</Emphasis>)-bdpp)}I(Ph) complex

Pt(diphosphine)X(aryl) complexes [diphosphine = 1,3-bis(diphenylphosphino)propane (dppp), 2,4-bis(diphenylphos phino)pentane (bdpp); aryl = phenyl, 2-thiophenyl; X = Cl, I] have been reacted with ethyl diazoacetate in chloroform. It has been revealed by in␣situ n.m.r. studies that the starting compounds insert the carbene, formed from ethyl diazoacetate, into the Pt–aryl group resulting in Pt(diphosphine)X{CH(aryl)COOC₂H₅}. Depending on the reaction conditions (reaction time, ratio of the reactants) and the ligands various side-reactions have been observed: (i) the formation of Pt(diphosphine)X₂ in chloroform, (ii) the insertion of the :CHCOOC₂H₅ fragment into the Pt–halide bond of the dihalogeno complexes Pt(diphosphine)X₂ resulting in the exclusive formation of Pt(diphosphine)X(CHXCOOC₂H₅). Diastereoselective insertion reactions have been observed in the presence of (S,S)-bdpp as diphosphine. The Pt{(S,S)-bdpp)}I(Ph) complex has been characterized by X-ray crystallography.     

Intramolecular Metal‐Free Oxidative Aryl–Aryl Coupling: An Unusual Hypervalent‐Iodine‐Mediated Rearrangement of 2‐Substituted N‐Phenylbenzamides

Hypervalent‐iodine‐mediated oxidative coupling of the two aryl groups in either 2‐acylamino‐N‐phenyl‐benzamides or 2‐hydroxy‐N‐phenylbenzamides, with concomitant insertion of the ortho‐substituted N or O atom into the tether, has been described for the first time. This unusual metal‐free rearrangement reaction involves an oxidative C(sp²)? C(sp²) aryl–aryl bond formation, cleavage of a C(sp²)? C(O) bond, and a lactamization/lactonization. Furthermore, unsymmetrical diaryl compounds can be easily obtained by removing the tether within the cyclized product.     

双-单齿芳香酰胺型配体桥联La3＋一维配位聚合物的合成与晶体结构

通过硝酸镧和双-单齿芳香酰胺型配体L {L＝1,4-双[(2'-苄胺甲酰基苯氧基)-甲基]苯}之间的反应得到了配位聚合物{[La(NO₃)₃]₂•L₃}_n, 并用X射线单晶衍射测定了配合物的晶体结构. 配合物为三斜晶系, _P1空间群, 晶胞参数a＝1.1298(2) nm, b＝1.2689(1) nm, c＝2.1030(3) nm, α＝81.189(9)°, β＝80.95(1)°, γ＝65.832(9)°, V＝2.7032(6) nm³, Z＝2, R＝0.0267, wR＝0.0679, La^3＋为9配位, 呈变形的三帽三角棱柱配位构型. 配合物通过配体的桥联作用形成一维环链相间的配位聚合结构, 由于相邻链间不存在氢键和π-π堆积作用, 所以配合物是以单链形式堆积排列.     

Cobalt‐Catalyzed Carbonylation of N‐Alkylbenzaldimines to ‘N‐Alkylphthalimidines’ (= 2,3‐Dihydro‐1H‐isoindol‐1‐ones) via Tandem C?H Activation and Cyclocarbonylation

The reaction of N‐alkylbenzaldimines with carbon monoxide (CO) in the presence of cobalt (Co) catalysts resulted in the formation of N‐alkylphthalimidines (Table 1). Their formation is proposed to occur by C? H activation of the aryl ring, migratory insertion of the hydride species into the benzaldimine functionality, CO coordination, and insertion into the Co? C bond, followed by reductive elimination of the N‐alkylphthalimidine and regeneration of the starting Co species (Scheme 4). Deuterium (²H)‐labeling NMR studies are consistent with this mechanism (Scheme 5).     

Programmable Amine Synthesis via Iterative Boron Homologation

The value of Matteson-type reactions has been increasingly recognized for developing automated organic synthesis. However, the typical Matteson reactions almost exclusively focus on homologation of carbon units. Here, we report the detailed development of sequential insertion of nitrogen and carbon atoms into boronate C−B bonds, which provides a modular and iterative approach to access functionalized tertiary amines. A new class of nitrenoid reagents is uncovered to allow direct formation of aminoboranes from aryl or alkyl boronates via N-insertion. The one-pot N-insertion followed by controlled mono- or double-carbenoid insertion has been realized with widely available aryl boronates. The resulting aminoalkyl boronate products can undergo further homologation and various other transformations. Preliminary success on homologation of N,N-dialkylaminoboranes and sequential N- and C-insertions with alkyl boronates have also been achieved. To broaden the synthetic utility, selective removal of a benzyl or aryl substituent permits access to secondary or primary amine products. The application of this method has been demonstrated in the modular synthesis of bioactive compounds and the programmable construction of diamines and aminoethers. A plausible reaction mechanism, supported by preliminary NMR (nuclear magnetic resonance) and computational studies, is also proposed.     

N-烷基/芳基-N'-(4-芳基噻唑-2-基)-N"-糖基胍的合成及生物活性研究

2,3,4,6-四-O-乙酰基-β-D-吡喃葡萄糖基异硫氰酸酯(1)与2-氨基-4-取代苯基噻唑(2a～2b)反应, 生成糖基硫脲衍生物3a～3b, 再在伯胺存在下经氯化汞脱硫, 得到一系列新的N-烷基/芳基-N'-(4-芳基噻唑-2-基)-N"-糖基胍类化合物(4a～4e, 5a～5e). 所有新化合物的结构均经IR, ¹H NMR, MS谱和元素分析证实, 所得产物均为β-构型. 生物活性测试结果表明, 化合物4b和5d对HIV-1 PR表现出了较高的抑制活性.     

1-[5-(1,3-二氧-4,5,6,7-四氢-1H-异吲哚-2-基)苯基]-3-取代脲衍生物的合成与除草活性研究

为了寻找高效低毒的原卟啉原氧化酶抑制剂(protox)类除草剂, 设计并合成了一系列1-[5-(1,3-二氧-4,5,6,7-四氢-1H-异吲哚-2-基)苯基]-3-取代脲类衍生物4a～4d和5a～5g. 化合物4a～4d经异氰酸酯法合成, 收率、纯度高; 化合物5a～5g利用固体光气一锅法合成, 反应时间短.所得化合物结构经¹H NMR, IR, 质谱和元素分析表征. 初步生物活性测试表明: 化合物4c, 5a, 5b, 5c在有效成分75 g/hm² 剂量下对苘麻、马刺苋、凹头苋等双子叶杂草表现出90%以上的防效.     

trans‐Selective Insertional Dihydroboration of a cis‐Diborene: Synthesis of Linear sp3‐sp2‐sp3‐Triboranes and Subsequent Cationization

The reaction of aryl‐ and amino(dihydro)boranes with dibora[2]ferrocenophane 1 leads to the formation 1,3‐trans‐dihydrotriboranes by formal hydrogenation and insertion of a borylene unit into the B=B bond. The aryltriborane derivatives undergo reversible photoisomerization to the cis‐1,2‐μ‐H‐3‐hydrotriboranes, while hydride abstraction affords cationic triboranes, which represent the first doubly base‐stabilized B₃H₄⁺ analogues.     

Palladium‐Catalyzed Multi‐Component Reactions of N‐Tosylhydrazones, 2‐Iodoanilines and CO2 towards 4‐Aryl‐2‐Quinolinones

A palladium‐catalyzed three‐component reaction between N‐tosylhydrazones, 2‐iodoanilines and atmospheric pressure CO₂ was developed whereby a tandem carbene migration insertion/lactamization strategy afforded 4‐aryl‐2‐quinolinones in moderate to good yields. Notably, a wide range of functional groups were tolerated in this procedure. This protocol features the simultaneous formation of four novel bonds; two C?C, one C=C and one C?N (amide), representing an efficient methodology for incorporation of CO₂ into heterocycles.