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1.
PPh3⋅HBr‐DMSO Mediated Expedient Synthesis of γ‐Substituted β,γ‐Unsaturated α‐Ketomethylthioesters and α‐Bromo Enals: Application to the Synthesis of 2‐Methylsulfanyl‐3(2 H)‐furanones
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Kanchan Mal Abhinandan Sharma Dr. Prakas R. Maulik Dr. Indrajit Das 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(3):662-667
An efficient chemoselective general procedure for the synthesis of γ‐substituted β,γ‐unsaturated α‐ketomethylthioesters from α,β‐unsaturated ketones has been achieved through an unprecedented PPh3?HBr‐DMSO mediated oxidative bromination and Kornblum oxidation sequence. The newly developed reagent system serves admirably for the synthesis of α‐bromoenals from enals. Furthermore, AuCl3‐catalyzed efficient access to 3(2H)‐furanones from the above intermediates under extremely mild conditions are described. 相似文献
2.
Xiuqin Dong Wen Yang Weimin Hu Jianwei Sun 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(2):670-673
The asymmetric fluorination of azolium enolates that are generated from readily available simple aliphatic aldehydes or α‐chloro aldehydes and N‐heterocyclic carbenes (NHCs) is described. The process significantly expands the synthetic utility of NHC‐catalyzed fluorination and provides facile access to a wide range of α‐fluoro esters, amides, and thioesters with excellent enantioselectivity. Pyrazole was identified as an excellent acyl transfer reagent for catalytic amide formation. 相似文献
3.
N‐Heterocyclic Carbene Catalyzed Enantioselective α‐Fluorination of Aliphatic Aldehydes and α‐Chloro Aldehydes: Synthesis of α‐Fluoro Esters,Amides, and Thioesters
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Dr. Xiuqin Dong Dr. Wen Yang Dr. Weimin Hu Prof. Dr. Jianwei Sun 《Angewandte Chemie (International ed. in English)》2015,54(2):660-663
The asymmetric fluorination of azolium enolates that are generated from readily available simple aliphatic aldehydes or α‐chloro aldehydes and N‐heterocyclic carbenes (NHCs) is described. The process significantly expands the synthetic utility of NHC‐catalyzed fluorination and provides facile access to a wide range of α‐fluoro esters, amides, and thioesters with excellent enantioselectivity. Pyrazole was identified as an excellent acyl transfer reagent for catalytic amide formation. 相似文献
4.
Meijuan Yuan Yewen Fang Li Zhang Xiaoping Jin Minjia Tao Qilin Ye Ruifeng Li Jinjian Li Hui Zheng Juejun Gu 《中国化学》2015,33(10):1119-1123
The first palladium‐catalyzed method for the arylation of α‐phosphonovinyl nonaflates is described. Using a catalyst comprised of Pd(OAc)2 and SPhos, terminal and internal α‐aryl vinylphosphonates could be efficiently accessed under mild conditions. The reaction features a broad coupling partner scope and tolerates many functional groups. 相似文献
5.
Zirconium(IV) chloride catalyzed efficient one-pot synthesis of β-amino/β-acetamido carbonyl compounds at room temperature is described. In the presence of ZrCl4, the three-component Mannich-type reaction via a variety of in situ generated aldimines, with various ketones, aromatic aldehydes and aromatic amines in ethanol, led to the formation of β-amino carbonyl compounds and the four-component Mannich-type reaction of aromatic aldehydes with various ketones, acetonitrile and acetyl chloride resulted in the corresponding β-acetamido carbonyl compounds in high to excellent yields. This methodology has also been applied towards the synthesis of dimeric β-amino/β-acetamido carbonyl compounds. 相似文献
6.
Lingjian Zhu Ning Lei Zhenyuan Miao Chunquan Sheng Chunlin Zhuang Jianzhong Yao Wannian Zhang 《中国化学》2012,30(1):139-143
A mild and efficient Knoevenagel‐Doebner reaction from malonic acid and a wide range of aldehydes was catalyzed by a catalytic system consisting of β‐alanine and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU), affording the corresponding (E)‐α,β‐unsaturated carboxylic acids in good to excellent yields and with high stereoselectivity. The advantage of the method is that the reaction could proceed smoothly at ambient temperature so that it can tolerate a variety of functional groups and avoid unnecessary side reactions. 相似文献
7.
《Journal of computational chemistry》2017,38(7):438-445
DFT calculations were conducted to pursue deeper understandings on the mechanism and the explicit role of trace water in the DBU‐catalyzed β‐amination of NBS to chalcone. Being different from previously proposed by Liang et al., a cooperative participation of both DBU and water is noticed in the preferred mechanism. The preferential mechanistic scenario assisted by water undergoes three major steps: the formation of succinimide and HBrO, concerted nucleophilic addition and H‐shift, and keto‐enol tautomerization. Moreover, we found that DBU‐HBrO is unnecessary in the third step and three‐water‐cluster assisted keto‐enol tautomerization is the most advantageous case. It is further noted that the catalytic position of the third water molecule and the proton shift orientation to some extent affect step 3 via O···H O and O H···π interactions, which is confirmed by AIM analysis. The computational results suggest that water molecules play pivotal roles as reactant, catalyst, and stabilizer to promote the reaction of chalcone and NBS. The origin of the more stable transition state structure in the rate‐determining step of DBU‐water catalyzed mechanism is ascribed to noncovalent interactions, halogen bond, and electrostatic interactions than DBU only ones. © 2017 Wiley Periodicals, Inc. 相似文献
8.
NHC‐Catalyzed Asymmetric Synthesis of Functionalized Succinimides from Enals and α‐Ketoamides
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Dr. Lei Wang Qijian Ni Marcus Blümel Tao Shu Prof. Dr. Gerhard Raabe Prof. Dr. Dieter Enders 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8033-8037
The efficient asymmetric synthesis of highly substituted succinimides from α,β‐unsaturated aldehydes and α‐ketoamides via NHC‐catalyzed [3+2] cycloaddition has been developed. The new scalable protocol significantly expands the utility of NHC catalysis for the synthesis of heterocycles and provides easy access to assemble a wide range of succinimides from simple starting materials. 相似文献
9.
Enantioselective Synthesis of Spirocyclohexadienones by NHC‐Catalyzed Formal [3+3] Annulation Reaction of Enals
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Santhivardhana Reddy Yetra Santigopal Mondal Subrata Mukherjee Dr. Rajesh G. Gonnade Dr. Akkattu T. Biju 《Angewandte Chemie (International ed. in English)》2016,55(1):268-272
The enantioselective synthesis of pyrazolone‐fused spirocyclohexadienones was demonstrated by the reaction of α,β‐unsaturated aldehydes with α‐arylidene pyrazolinones under oxidative N‐heterocyclic carbene (NHC)catalysis. This atom‐economic and formal [3+3] annulation reaction proceeds through a vinylogous Michael addition/spiroannulation/dehydrogenation cascade to afford spirocyclic compounds with an all‐carbon quaternary stereocenter in moderate to good yields and excellent ee values. Key to the success of the reaction is the cooperative NHC‐catalyzed generation of chiral α,β‐unsaturated acyl azoliums from enals, and base‐mediated tandem generation of dienolate/enolate intermediates from pyrazolinones. 相似文献
10.
A novel Cu(OAc)2·H2O catalyzed coupling reaction of N‐substituted‐2‐iodobenzamides with malononitrile to afford N‐substituted‐3‐amino‐4‐cyano‐isoquinoline‐1(2H)‐ones is described. The reaction proceeded in DMSO at 90°C for 5 h in nitrogen without external ligands. 相似文献
11.
Synthesis of α,α‐Difluoromethylene Alkynes by Palladium‐Catalyzed gem‐Difluoropropargylation of Aryl and Alkenyl Boron Reagents
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Yan‐Bo Yu Guo‐Zhen He Prof. Dr. Xingang Zhang 《Angewandte Chemie (International ed. in English)》2014,53(39):10457-10461
gem‐Difluoropropargyl bromides are versatile intermediates in organic synthesis, but have rarely been employed in transition‐metal‐catalyzed cross‐coupling reactions. The first palladium‐catalyzed gem‐difluoropropargylation of organoboron reagents with gem‐difluoropropargyl bromides is now reported. The reaction proceeds under mild reaction conditions with high regioselectivity; it features a broad substrate scope and excellent functional‐group compatibility and thus provides an attractive approach for the synthesis of complex fluorinated molecules, in particular for drug discovery and development. 相似文献
12.
Jean‐Baptiste Gualtierotti Xavier Schumacher Dr. Patrice Fontaine Dr. Géraldine Masson Dr. Qian Wang Prof. Dr. Jieping Zhu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(46):14812-14819
Mild and general alumina‐promoted hydrolysis conditions for converting α‐iminonitriles into carboxamides have been developed. In combination with the oxidative three‐component Strecker reaction, the one‐pot direct amidation of aldehydes and alcohols is reported. Subsequently, an Yb(OTf)3‐catalyzed Michael addition of thiols to α,β‐unsaturated α‐iminonitriles is reported for the synthesis of β‐mercapto‐α‐iminonitriles. The successful integration of an oxidative Strecker reaction, thio‐Michael addition, and neutral‐alumina‐promoted hydrolysis of β‐mercapto‐α‐iminonitriles into a three‐component one‐pot process allowed us to develop the direct conversion of amines, aldehydes, and thiols into β‐mercaptoamides. All of these procedures were applicable to aromatic and aliphatic amines and aldehydes. 相似文献
13.
Benito Alcaide Prof. Dr. Pedro Almendros Dr. Teresa Martínez del Campo Rocío Carrascosa 《化学:亚洲杂志》2008,3(7):1140-1145
A mild, palladium(II)‐catalyzed reaction of α‐allenols with α‐allenic esters in a heterocyclization/cross‐coupling sequence, applicable to a wide range of substitution patterns, has been developed for the preparation of 2,3,4‐trifunctionalized 2,5‐dihydrofurans. Our studies indicate high levels of chemo‐ and regiocontrol. The possibility of using optically active substrates as well as substrates of increased steric demand, such as tertiary α‐allenols, makes this novel sequence of heterocyclization/cross‐coupling an attractive method in organic synthesis. The current mechanistic hypothesis invokes a regiocontrolled palladium(II)‐mediated intramolecular oxypalladation of the free allenol component, that then undergoes a cross‐coupling reaction with the allenic ester partner, followed by a trans‐β‐deacyloxypalladation with concomitant regeneration of the PdII species. 相似文献
14.
《中国化学》2018,36(8):712-715
Herein, two efficient palladium‐catalyzed intermolecular oxidative coupling reactions of (Z)‐enamines with isocyanides via selective β‐C(sp2)‐H and/or C=C bond cleavage have been developed, leading to controllable chemodivergent and stereoselective construction of a wide range of (E)‐β‐carbamoylenamine derivatives containing strong intramolecular hydrogen bonds. Furthermore, possible reaction pathways for these transformations are proposed on the basis of preliminary mechanism studies. 相似文献
15.
Dr. Tuo Jiang Dr. Xu Quan Dr. Can Zhu Prof. Dr. Pher G. Andersson Prof. Dr. Jan‐E. Bäckvall 《Angewandte Chemie (International ed. in English)》2016,55(19):5824-5828
We report a palladium‐catalyzed oxidative functionalization of alkynes to generate α‐acetoxylated enones in one step. A range of functional groups are well‐tolerated in this reaction. Mechanistic studies, including the use of 18O‐labeled DMSO, revealed that the ketone oxygen atom in the product originates from DMSO. 相似文献
16.
Ya Chen Yixiao Pan Yan‐Mei He Qing‐Hua Fan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(47):16987-16990
A highly enantioselective iridium‐ or ruthenium‐catalyzed intermolecular reductive amination/asymmetric hydrogenation relay with 2‐quinoline aldehydes and aromatic amines has been developed. A broad range of sterically tunable chiral N,N′‐diaryl vicinal diamines were obtained in high yields (up to 95 %) with excellent enantioselectivity (up to >99 % ee). The resulting chiral diamines could be readily transformed into sterically hindered chiral N‐heterocyclic carbene (NHC) precursors, which are otherwise difficult to access. The usefulness of this synthetic approach was further demonstrated by the successful application of one of the chiral vicinal diamines and chiral NHC ligands in a transition‐metal‐catalyzed asymmetric Suzuki–Miyaura cross‐coupling reaction and asymmetric ring‐opening cross‐metathesis, respectively. 相似文献
17.
Palladium(II)‐N‐heterocyclic carbene complexes: synthesis,characterization and catalytic application
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N‐Heterocyclic carbenes (NHCs) are of great importance and are powerful ligands for transition metals. A new series of sterically hindered benzimidazole‐based NHC ligands (LHX) ( 2a , 2b , 2c , 2d , 2e , 2f ), silver–NHC complexes ( 3a , 3b , 3c , 3d , 3e , 3f ) and palladium–NHC complexes ( 4a , 4b , 4c , 4d , 4e , 4f ) have been synthesized and characterized using appropriate spectroscopic techniques. Studies have focused on the development of a more efficient catalytic system for the Suzuki coupling reaction of aryl chlorides. Catalytic performance of Pd–NHC complexes and in situ prepared Pd(OAc)2/LHX catalysts has been investigated for the Suzuki cross‐coupling reaction under mild reaction conditions in aqueous N,N‐dimethylformamide (DMF). These complexes smoothly catalyzed the Suzuki–Miyaura reactions of electron‐rich and electron‐poor aryl chlorides. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
18.
Xiaoge Yang Zhuqing Liu Prof. Chenglin Sun Prof. Dr. Jiping Chen Prof. Dr. Zhengkun Yu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(40):14085-14094
Efficient palladium‐catalyzed cross‐coupling reactions of the internal olefins α‐cyanoketene dithioacetals with a variety of olefins were achieved in dioxane/HOAc/DMSO (9:3:1 v/v/v) under air atmosphere or by means of AgOAc as the terminal oxidant. Electron‐deficient terminal olefins reacted to form the linear diene derivatives with air as the oxidant. Styrenes underwent the cross‐coupling to give both the linear and branched dienes when using AgOAc as the oxidant. Unactivated cyclic and linear internal olefin substrates both reacted in the presence of a catalytic amount of benzoquinone in air to produce skipped dienes. The typical products were structurally confirmed by X‐ray crystallography. 相似文献
19.
Selective α-Bromination of β-Keto Esters in Reusable PEG-400 under Mild and Catalyst-free Conditions
An efficient bromination protocol for the synthesis of α-bromo-β-keto esters has been developed. In PEG-400 (poly(ethylene glycol-400)), a variety of β-keto esters were treated with NBS (N-bromosuccinimide) at room temperature to selectively afford the corresponding α-monobromination products in excellent yields. It is noteworthy that the reaction was conducted under mild, environmentally benign and catalyst-free conditions. 相似文献
20.
An easy and efficient method for the aminobromination of β,β‐dicyanostyrene derivatives with NBS as the aminobrominating reagent in CH3CN catalyzed by NaOAc (10 mol%) is developed. This protocol provides convenient process to convert β,β‐dicyanostyrene derivatives into the vicinal haloamines with full regiospecificity and high stereoselectivety in the ice‐water bath in air. The reaction is high efficient in yielding the corresponding aminobrominated products in excellent yields (up to 95%) under these conditions. The outcome indicated that the reaction has an electrophilic addition feature. 12 Eexamples of β,β‐dicyanostyrene derivatives have been investigated. 相似文献