Pd-Catalyzed Asymmetric 5-exo-trig Cyclization/Cyclopropanation/Carbonylation of 1,6-Enynes for the Construction of Chiral 3-Azabicyclo[3.1.0]hexanes

We herein disclose a mild and efficient access to chiral 3-azabicyclo[3.1.0]hexanes via a Pd-catalyzed asymmetric 5-exo-trig cyclization/cyclopropanation/carbonylation of 1,6-enynes. Various nucleophiles, such as alcohols, phenols, amines and water, are well compatible with the reaction system. This reaction forms three C−C bonds, two rings, two adjacent quaternary carbon stereocenters as well as one C−O/C−N bond with excellent regio- and enantioselectivities. The products could be further functionalized to generate a library of 3-azabicyclo[3.1.0]hexane frameworks.     

通过"双离子键"固载于季鏻盐聚合物的[Rh(CO)I3]2–物种在多相乙醇羰基化中的应用

贵金属物种(Rh或Ir络合物)在均相羰基化和氢甲酰化催化过程得到了广泛的应用,但始终存在分离繁琐等问题,其均相多相化可很大程度上简化分离操作,故一直广受重视.单位点催化剂因其具有可与均相相比拟的较高金属利用率和选择性而成为均相多相化的重要研究方向之一.研究发现,在碘物种存在的情况下用于固载金属物种的配位键容易断裂,进而导致金属物种的流失,而通过离子键固载的[Rh(CO)₂I₂]^–物种更加稳定,比如著名的甲醇羰基化“Acetica^TM”工艺中,[Rh(CO)₂I₂]^–负一价阴离子物种是以离子键的方式固定在带有阳离子骨架的甲基化聚乙烯吡啶树脂上.与甲醇羰基化过程类似的乙醇羰基化过程是生产重要化工中间体丙酸的主要途径之一,但该过程的均相多相化始终存在着稳定性差这一关键问题.为了解决这一问题,基于之前将固载于季鏻盐聚合物的[Rh(CO)I₃]^2–应用于甲醇羰基化的工作,我们将类似的季鏻盐聚合物固载Rh基催化剂Rh-TPISP用于多相乙醇羰基化过程,通过多种表征进一步证明了Rh物种和P物种结构,并提出了“双离子键”模型.P的K边XANES证明了聚合物TPISP的季鏻化阳离子骨架特征.HAADF-STEM测试表明Rh-TPISP中的Rh呈现单位点分散的状态.Rh的XPS和XANES结果证明了Rh-TPISP中Rh物种的价态介于0~+1.通过EXAFS的拟合解析给出了[Rh(CO)I₃]^2–活性中心结构.由于[Rh(CO)₂I₂]^–为经典的羰基化活性中心,为了进一步证明该结构的正确性,我们将Rh-TPISP的EXAFS和IR谱图与标样[PPh3Et]⁺[Rh(CO)₂I₂]^–对比发现:在EXAFS谱图中,Rh-TPISP中的Rh-C峰高低于[PPh3Et]+[Rh(CO)₂I₂]^–的Rh-C峰高,而Rh-TPISP中的Rh-I峰高高于[PPh3Et]+[Rh(CO)₂I₂]^–的Rh-I峰高,这就说明Rh-TPISP中Rh物种的Rh-C配位数小于2,而Rh-I配位数大于2;在IR谱图中,标样[PPh3Et]+[Rh(CO)₂I₂]^–中有两个羰基振动峰,与该物种的两个Rh-C配位键相符,而Rh-TPISP中的只有一个羰基振动峰,说明Rh-C配位数为1.因此,Rh-TPISP催化剂的季鏻盐骨架中的每个P物种带有一个正电荷,每个带有两个负电荷的[Rh(CO)I₃]^2–通过与两个[P]⁺的静电作用进行固载,形成“双离子键”结构.该催化剂在固定床乙醇羰基化过程中表现出优异的羰基化活性、选择性和稳定性.在3.5 MPa、195 oC反应近1000 h后,Rh-TPISP催化剂TOF保持在约350 h–1,丙酰基选择性为95%以上,高出所有文献报道的均相和多相乙醇羰基化活性.其较高的活性主要是因为[Rh(CO)I₃]^2–比传统Rh活性相[Rh(CO)₂I₂]^–具有更强的富电子性,而较高的稳定性主要是由于“双离子键”这种强静电作用比“AceticaTM”工艺中“单离子键”更有利于Rh物种的固载.故Rh-TPISP催化剂中的“双离子键”对其优异的催化性能具有极其重要的作用,对后续多相乙醇羰基化的发展具有重要意义.     

Synthesis of (+)-boronolide and (+)-deacetylboronolide using Pd-catalyzed carbonylation and lactonization

(+)-Boronolide and (+)-deacetylboronolide were synthesized using Pd-catalyzed CO insertion and lactonization as the key step. As to the ¹³C NMR data of (+)-deacetylboronolide, the assignment at C-6 position should be revised.     

Catalytic Carbonylation and Carboxylation of Organosulfur Compounds via C−S Cleavage

Transition‐metal‐catalyzed carbonylation with CO gas occupies a privileged position in organic synthesis for the synthesis of carbonyl compounds. Although this attractive and useful chemistry has led many researchers to investigate carbonylative transformations of various organic (pseudo)halides, C?S‐cleaving carbonylation of organosulfur compounds has been fairly limited. Recently, a broad spectrum of C?S‐cleaving transformations has been emerging in the field of cross‐coupling. In light of the importance of carbonyl compounds as well as considerable advancement for employing organosulfur compounds as competent surrogates of (pseudo)halides, carbonylative transformations of C?S bonds should be of high value. This Minireview focuses on catalytic C?S carbonylation of organosulfur compounds with CO or its equivalents. In addition, reductive carboxylation of C?S bonds with CO₂ is described.     

尿素羰基化作用研究进展

综述了尿素作为羰基化试剂合成氨基酸酯或碳酸酯类化合物及脲类化合物的研究进展,详细讨论了合成反应中所涉及的催化剂、反应机理和工艺条件,指出通过尿素醇解或胺解反应合成相应化合物是一条绿色工艺路线,具有广阔应用前景.     

Synthesis of (E)-2-(1-ferrocenylmethylidene)malonic acid derivatives by a cobalt-catalyzed domino reaction of ethyl diazoacetate, carbon monoxide and ferrocenylimines

The domino reaction of ethyl diazoacetate, carbon monoxide and ferrocenylimines was investigated in the presence of Co₂(CO)₈ as catalyst. In most cases the main products are 2-(1-ferrocenylmethylidene) malonates formed by an N(1)-C(4) cleavage of the primarily derived β-lactams. The latter compounds could only be isolated when the reaction was carried out at relatively low CO pressure, using an excess of ethyl diazoacetate. trans-N-(tert-Butyl)-3-ethoxycarbonyl-4-ferrocenyl-β-lactam proved to be the most stable one among these compounds and could be isolated in 55% yield. N-alkyl β-lactams were shown to undergo acidic cleavage leading to the E isomers of 2-(1-ferrocenylmethylidene) malonates as the main products. The structures of the two new compounds, (E)-2-ethoxycarbonyl-3-ferrocenyl-N-((R)-1-phenylethyl)-2-propenamide and trans-N-(tert-butyl)-3-ethoxycarbonyl-4-ferrocenyl-β-lactam were confirmed by X-ray crystallography. The relative thermodynamical stability of the products as well as the energetics of the acid-mediated cleavage of the β-lactam ring was elucidated with DFT calculations.     

Convenient palladium-catalyzed aminocarbonylation of anilines to N-arylbenzamides

The first one-pot diazotization/aminocarbonylation reaction of anilines to benzamides has been developed. In the presence of commercially available palladium acetate/P(o-Tolyl)₃ as the catalyst system without base at low temperature (50 °C) a variety of amides were synthesized in moderate to good yields.     

碳一化工路线制备乙二醇研究进展

乙二醇(EG)是一种重要的化工原料,主要用来生产新型聚酯纤维.近年来由于我国聚酯产业发展迅速,极大的推动了对乙二醇的需求.碳一化工路线以资源丰富、价格便宜的天然气或煤为原料合成乙二醇,有着诱人的工业化前景.综述了以合成气为原料合成乙二醇的研究进展,包括合成气直接合成法、甲醛羰化法、CO偶联法、甲醛氢甲酰化法以及甲醛缩合法等.     

微米及纳米丝光沸石分子筛上二甲醚羰基化反应的积碳分析

对比研究了在传统微米尺寸和新结构纳米丝光沸石催化剂上二甲醚羰基化合成乙酸甲酯的反应行为.结果表明,通过减小分子筛的尺寸到纳米水平,可以有效提高反应物和产物到达或者脱离反应活性位的效率,从而提高了二甲醚的转化率;更重要的是,抑制了硬积碳的生成,使催化剂保持了更高的稳定性.     

5′-O-TBDMS-3′-O--(1H-Imidazole-1-Thiocarbonyl)thymidine: A Novel Intermediate for the Synthesis of 2,3′-Anhydrothymidine

Thermal or base-promoted conversion of 5′-O-TBDMS-3′-O-(1H-imidazole-1-thiocarbonyl)thymidine (1) afforded 5′-O-TBDMS-2,3′-anhydro-thymidine (2), a pivotal intermediate for the transformation of the 3′-hydroxy group of 2′-deoxyribonucleosides, in high yield.