- NHC-catalyzed [4 + 2] annulations of allenoates and 2,3-dioxopyrrolidine derivatives
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A facile NHC-catalyzed [2 + 4] annulation of allenoates with 2,3-dioxypyrrolidine derivatives was discovered, which paved a new avenue for the construction of highly substituted pyranopyrrole with moderate to good yields, high atom economy and mild reaction conditions. This journal is
- Chen, Yangxu,Li, Tuanjie,Lu, Fangfang,Song, Xue,Yao, Changsheng,Yu, Chenxia,Zhang, Kai
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supporting information
p. 1219 - 1225
(2022/02/21)
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- Organocatalyzed [2+2] Cycloaddition Reactions between Quinone Imine Ketals and Allenoates
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A new cycloaddition reaction of quinone imine ketals (QIKs), which could be utilized to the construction of functionalized azaspirocyclics under mild conditions, is described. This transformation involved a [2+2] cycloaddition reaction between QIKs and allenoates catalyzed by DABCO, and then treatment with 1 N HCl in one-pot. The strategy could provide a practical route to access azetidine-fused spirohexadienones in good to excellent yields and with high E -selectivity.
- Liu, Teng,He, Chixian,Wang, Fan,Shen, Xiang,Li, Yongqin,Lang, Man,Li, Guijun,Huang, Chao,Cheng, Feixiang
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p. 518 - 526
(2020/10/12)
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- Phosphine catalyzed [3+2] cyclization/Michael addition of allenoate with CS2to form 2-thineyl vinyl sulfide
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We have developed a DPPE-catalyzed three molecular two component tandem reaction of γ-substituted allenoate and CS2 to construct 2-thineyl vinyl sulfide through phosphine catalyzed [3+2] cyclization followed by Michael addition. The synthetic value of the
- Fei, Weihong,Xu, Ping,Hou, Jie,Yao, Weijun
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supporting information
p. 11669 - 11672
(2020/10/19)
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- Indolizine derivative and preparation method thereof
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The invention discloses an indolizine derivative and a preparation method thereof. The indolizine derivative is prepared from pyridinium bromide and allenic acid ester through [3+2] cycloaddition reaction in a reaction solvent under the action of an inorganic base catalyst and a Lewis base promoter in a nitrogen atmosphere. The reaction substrate of the preparation method is simple, easy to synthesize and low in price; wherein the [3+2] cycloaddition reaction has the advantages of mild reaction conditions, high reaction efficiency, high indolizine derivative yield and high atom economy. Therefore, the indolizine derivative has the advantages of no catalyst residue, high purity and high application value.
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Paragraph 0060; 0065-0067; 0072; 0076-0077; 0081; 0085-0086
(2020/11/23)
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- NHC-Catalyzed Aldol-Like Reactions of Allenoates with Isatins: Regiospecific Syntheses of γ-Functionalized Allenoates
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An N-heterocyclic carbene (NHC) catalyzed γ-specific aldol-like reaction between allenoates and isatins has been achieved under mild conditions, giving trisubstituted allene derivatives bearing isatin moiety in moderate to good yields with high diastereoselectivity and excellent atom efficiency. The DFT computations indicated that the formation of the γ-adduct was more energetically favorable than that of the α-adduct. The result reported herein opens a new route for NHC-promoted allenoate-involved reaction.
- Li, Sha,Tang, Ziwei,Wang, Yang,Wang, Dan,Wang, Zhanlin,Yu, Chenxia,Li, Tuanjie,Wei, Donghui,Yao, Changsheng
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supporting information
p. 1306 - 1310
(2019/02/26)
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- Phosphine-catalyzed dearomative [3+2] annulation of 3-nitroindoles and allenoates
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The efficient phosphine-catalyzed dearomative [3+2] annulation of 3-nitroindoles with allenoates has been successfully developed, providing a facile access to cyclopenta[b]indolines with good to excellent yields and high diastereoselectivities. This strategy features mild reaction conditions, high functional group tolerance, and scalability. Additionally, the 2-nitrobenzofuran and 2-nitrobenzothiophene were good dearomative [3+2] annulation partners.
- Liu, Kui,Wang, Gang,Cheng, Shao-Jie,Jiang, Wen-Feng,He, Cheng,Ye, Zhi-Shi
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supporting information
p. 1885 - 1890
(2019/06/21)
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- Sulfinate-Engaged Nucleophilic Addition Induced Allylic Alkylation of Allenoates
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A strategically novel Pd-catalyzed nucleophilic addition induced allylic alkylation reaction (NAAA) of allenoates has been successfully accomplished. By judiciously integrating ZnCl2-promoted Michael addition with Pd-catalyzed allylic alkylation, allenoates readily undergo allyl-sunfonylation at the internal double bond, thus providing a straightforward avenue for the rapid assembly of a host of structurally diversified α-allyl-β-sufonylbut-3-enoate derivatives. The success of this transformation profits from a delicate control of the reaction kinetic of each elementary step, thanks to the synergistic interaction of Pd/Zn bimetallic system, thus suppressing either direct allylic sulfonylation or premature quenching of therein in situ generated ester enolate intermediate. Furthermore, by expanding the scope of workable Michael acceptor beyond those previously required doubly activated ones, such as methylenemalononitrile, the present work substantially enriches the repertoire of NAAA reactions.
- Lin, Ling-Zhi,Che, Yuan-Yuan,Bai, Peng-Bo,Feng, Chao
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supporting information
p. 7424 - 7429
(2019/10/02)
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- A Scaffold-Diversity Synthesis of Biologically Intriguing Cyclic Sulfonamides
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A “branching–folding” synthetic strategy that affords a range of diverse cyclic benzo-sulfonamide scaffolds is presented. Whereas different annulation reactions on common ketimine substrates build the branching phase of the scaffold synthesis, a common hydrogenative ring-expansion method, facilitated by an increase of the ring-strain during the branching phase, led to sulfonamides bearing medium-sized rings in a folding pathway. Cell painting assay was successfully employed to identify tubulin targeting sulfonamides as novel mitotic inhibitors.
- Zimmermann, Stefan,Akbarzadeh, Mohammad,Otte, Felix,Strohmann, Carsten,Sankar, Muthukumar Gomathi,Ziegler, Slava,Pahl, Axel,Sievers, Sonja,Kumar, Kamal
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supporting information
p. 15498 - 15503
(2019/11/16)
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- Stereoselective Synthesis of Functionalized Benzooxazepino[5,4- a] isoindolone Derivatives via Cesium Carbonate Catalyzed Formal [5 + 2] Annulation of 2-(2-Hydroxyphenyl)isoindoline-1,3-dione with Allenoates
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In this work, we present a strategy for the stereoselective synthesis of functionalized benzooxazepino[5,4-a]isoindolone derivatives via a Cs2CO3-catalyzed domino β-addition and γ-aldol reaction of 2-(2-hydroxyphenyl)isoindoline-1,3-dione derivatives with allenoates, which offers an avenue for a combination of the structural unity between benzooxazepine and isoindolone motifs in synthetically useful yields with high stereoselectivities under mild conditions. Remarkably, it is the first example of highly stereoselective Cs2CO3-catalyzed formal [5 + 2] annulation of 2-(2-hydroxyphenyl)isoindoline-1,3-dione with allenoates.
- Yao, Chao,Bao, Yishu,Lu, Tao,Zhou, Qingfa
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supporting information
p. 2152 - 2155
(2018/04/30)
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- Nickel-catalyzed, ligand-free, diastereoselective synthesis of 3-methyleneindan-1-ols
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Nickel-catalyzed, highly diastereoselective annulations between activated allenes and 2-acetylarylboronic acid or 2-formylarylboronic acids are reported. No ligand for nickel is required, and the reactions proceed efficiently at room temperature to give a broad range of substituted 3-methyleneindan-1-ols. Preliminary results of an enantioselective variant are also described.
- Panchal, Heena,Clarke, Christopher,Bell, Charles,Karad, Somnath Narayan,Lewis, William,Lam, Hon Wai
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supporting information
p. 12389 - 12392
(2018/11/20)
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- Phosphine-Catalyzed [8 + 2]-Annulation of Heptafulvenes with Allenoates and Its Asymmetric Variant: Construction of Bicyclo[5.3.0]decane Scaffold
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In this paper, a phosphine-catalyzed [8 + 2]-annulation of heptafulvene with allenoates has been achieved under mild conditions, giving functionalized bicyclo[5.3.0]decane derivatives in moderate to excellent yields. Using chiral phosphine as the catalyst, optically active products were obtained in moderate to high yields with excellent enantioselectivities.
- Gao, Zhenzhen,Wang, Chang,Zhou, Leijie,Yuan, Chunhao,Xiao, Yumei,Guo, Hongchao
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supporting information
p. 4302 - 4305
(2018/07/29)
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- Phosphine-Catalyzed Domino β/γ-Additions of Benzofuranones with Allenoates: A Method for Unsymmetrical 3,3-Disubstituted Benzofuranones
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A phosphine-catalyzed domino process of benzofuranones with allenoates has been developed which furnishes highly functionalized unsymmetrical 3,3-disubstituted benzofuranones in synthetically useful yields. The mechanism for the transformation is a tandem β-umpolung/γ-umpolung process.
- Huang, Zhusheng,Yang, Xiuqin,Yang, Fulai,Lu, Tao,Zhou, Qingfa
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supporting information
p. 3524 - 3527
(2017/07/17)
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- Efficient and regioselective one-pot synthesis of S-vinyl dithiocarbamates from electron-deficient allenes, amines and CS2
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A novel and efficient one-pot procedure for the synthesis of S-vinyl dithiocarbamates from electron-deficient allenes, amines and CS2was presented. The reactions proceed at room temperature for 10–30?min without any catalyst to afford the products in high yields, excellent regioselectivity and stereoselectivity.
- Li, Ridong,Leng, Penglin,Liu, Bin,Wang, Xin,Ge, Zemei,Li, Runtao
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supporting information
p. 5707 - 5712
(2016/08/23)
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- Transpositive Tandem Annulation of Phthalides with Allene Carboxylates: Regioselective Synthesis of Arylnaphthalene Lignans
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Allene carboxylates, scarcely used as Michael acceptors, serve as acceptors in the annulation with phthalides in the presence of LDA and provide a one-pot synthesis of naphtho[c]furanones in very good yields. This tandem annulation is proposed to proceed
- Mal, Dipakranjan,Jana, Supriti
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p. 11857 - 11865
(2016/12/09)
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- Quinidine-Catalysed Enantioselective Synthesis of 6- and 4-Trifluoromethyl-Substituted Dihydropyrans
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The cinchona alkaloid-catalysed enantioselective formal [4+2] cycloaddition of ethyl 2,3-butadienoate with a range of 1,1,1-trifluoro- and 4,4,4-trifluorobutenones is investigated for the preparation of stereodefined 6- and 4-trifluoromethyl-substituted dihydropyrans. Quinidine proved to be the optimal catalyst, generating the desired products in up to 98 % ee and 81 % yield. Stereo- and chemoselective derivatization of the dihydropyrans through hydrogenation is explored.
- Kasten, Kevin,Cordes, David B.,Slawin, Alexandra M. Z.,Smith, Andrew D.
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supporting information
p. 3619 - 3624
(2016/07/28)
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- Copper-catalyzed, C-C coupling-based one-pot tandem reactions for the synthesis of benzofurans using o-iodophenols, acyl chlorides, and phosphorus ylides
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One-pot reactions involving acyl chlorides, phosphorus ylides, and o-iodophenols with copper catalysis have been established for the rapid synthesis of functionalized benzofurans. With all of these easily available and stable reactants, the construction o
- Liu, Yunyun,Wang, Hang,Wan, Jie-Ping
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p. 10599 - 10604
(2015/02/19)
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- AlCl3-promoted selective michael addition with allenoate and methyleneindolinone: Synthesis of spirocyclic oxindole by using allenoate as a four-carbon component building block
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The AlCl3-promoted cyclization of readily available allenoates with methyleneindolinone is disclosed. The present strategy provides a rapid access to spirocyclic oxindole-cyclohexenones in an efficient manner. Remarkably, the allenoate is implemented as a four-carbon (4C) component to form the ring, which shows high synthetic efficiency. Flexibility of this method allows quick synthesis of spirocyclic oxindole-dihydropyrans by varying one of the components. It is also noteworthy that AlCl3 serves as the chlorine source as well as an effective catalyst to facilitate this interesting transformation.
- Xu, Shibo,Li, Chunju,Jia, Xueshun,Li, Jian
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p. 11161 - 11169
(2015/01/08)
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- Multicomponent reaction to construct spirocyclic oxindoles with a Michael (triple Michael)/cyclization cascade sequence as the key step
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Multicomponent cycloadditions with readily available isocyanides, allenoates, and isatylidene malononitriles are disclosed. This reaction, which does not require the aid of any catalyst, allows the efficient syntheses of spirocyclic oxindoles with excellent regioselectivity. Reactions with ethyl 2,3-butadienoate and various structurally diverse α- and γ-substituted allenoates are also fully explored. Remarkably, we have shown that the usual three-component process can be further developed into an unprecedented four-component cycloaddition in the presence of water, which provides a new strategy to access highly unusual tricyclic oxindoles. From a synthetic point of view, this protocol is very interesting considering the high level of complexity reached in one step. The mechanism is thought to proceed by a triple Michael/cyclization process by using allenoate as a three carbon atom component (3 C). Furthermore, multicomponent reaction with γ-substituted allenoate also results in a very interesting conversion. In such cases, the unusual cleavage of the "C=C" double bond of isatylidene malononitrile and one of the "C=C" double bonds of allenoate is always observed. Multiply your chemistry! Multicomponent reactions with readily available isocyanides, allenoates, and isatylidene malononitriles are disclosed. This protocol provides a synthetic route to an exocyclic double bond containing a spirocyclic ring in an efficient manner with excellent regioselectivity (see scheme). Copyright
- Li, Jian,Wang, Ning,Li, Chunju,Jia, Xueshun
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supporting information; experimental part
p. 9645 - 9650
(2012/09/07)
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- Phosphine-catalyzed annulations of azomethine imines: Allene-dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] pathways
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In this paper we describe the phosphine-catalyzed [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] annulations of azomethine imines and allenoates. These processes mark the first use of azomethine imines in nucleophilic phosphine catalysis, producing dinitrogen
- Na, Risong,Jing, Chengfeng,Xu, Qihai,Jiang, Hui,Wu, Xi,Shi, Jiayan,Zhong, Jiangchun,Wang, Min,Benitez, Diego,Tkatchouk, Ekaterina,Goddard, William A.,Guo, Hongchao,Kwon, Ohyun
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supporting information; experimental part
p. 13337 - 13348
(2011/10/09)
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- Regio- and stereoselective copper-catalyzed β-borylation of allenoates by a preactivated diboron
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A mild and efficient copper-catalyzed borylation of electron deficient allenoates using an sp2-sp3 mixed hybridized diboron regioselectively installs a boron moiety on the β-position with exclusive (Z)-double bond geometry.
- Thorpe, Steven B.,Guo, Xi,Santos, Webster L.
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supporting information; scheme or table
p. 424 - 426
(2011/02/28)
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- Silver hexafluoroantimonate-catalyzed three-component [2+2+1]cycloadditions of allenoates, dual activated olefins, and isocyanides
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The intermolecular [2+2+1]multicomponent cycloadditions from readily available allenoates, dual activated olefins and isocyanides catalyzed by silver hexafluoroantimonate were studied. This protocol allowed the syntheses of highly functionalized five-membered carbocycles with exclusive regioselectivity and stereoselectivity in an efficient and atom-economical manner.
- Li, Jian,Liu, Yuejin,Li, Chunju,Jia, Xueshun
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supporting information; experimental part
p. 913 - 917
(2011/06/18)
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- Syntheses of spirocyclic oxindole-butenolides by using three-component cycloadditions of isocyanides, allenoates, and isatins
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Spiro workflow! Efficient syntheses of spirocyclic oxindole-butenolides from readily available isocyanides, allenoates, and isatins are disclosed (see scheme; R1=alkyl, aryl; R2=halide, nitro, methoxy; PG=protecting group). This protocol also allows the insertion of carbon monoxide into organic molecules without the aid of a transition-metal catalyst after the hydrolysis process. Copyright
- Li, Jian,Liu, Yuejin,Li, Chunju,Jia, Xueshun
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supporting information; experimental part
p. 7409 - 7413
(2011/08/05)
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- Triphenylphosphine-catalyzed [3+2] cycloaddition of allenoate and active olefins: Syntheses of spirooxindole derivatives
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A series of spiro compounds was achieved by triphenylphosphine-catalyzed [3+2] cycloaddition between active methylenemalononitrile and ethyl 2,3-butadienoate. Careful investigation showed that the present method had high regioselectivity. The products have a spirooxindole skeleton, which is a motif common in many natural products and pharmaceutically active compounds. Georg Thieme Verlag Stuttgart - New York.
- Guo, Shanyan,Wang, Rendong,Li, Jian,Li, Chunju,Deng, Hongmei,Jia, Xueshun
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supporting information; experimental part
p. 2256 - 2258
(2011/11/05)
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- Allene carboxylates as dipolarophiles in Rh-catalyzed carbonyl ylide cycloadditions
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Face-to-face: Allene carboxylates can serve as efficient dipolarophiles for Rh-catalyzed carbonyl ylide cycloadditions (see scheme). The endo and exo products arise from cycloaddition on the same face of the allene, but opposite faces of the dipole. This facial selectivity results in the formation of two of the four possible diastereomers.
- Rout, Laxmidhar,Harned, Andrew M.
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supporting information; experimental part
p. 12926 - 12928
(2010/05/19)
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- Total synthesis of (±)-kellermanoldione: stepwise cycloaddition of a functionalized diene and allenoate
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Figur Presented The total synthesis of the diterpene kellermanoldione 1 is reported. Stepwise [4 + 2] cycloaddition of the ketal diene 8 and the allenoste 3 afforded the exo adduct 10x as the major product. It was converted into 1 via six steps, among them a key nonconjugative hydrolysis of a γ-methylene silyl enol ether
- Jung, Michael E.,Cordova, Jesus,Murakami, Masayuki
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supporting information; experimental part
p. 3882 - 3885
(2009/12/03)
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- Selective one-pot synthesis of allenyl and alkynyl esters from β-ketoesters
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(Chemical Equation Presented) A convenient method is described for the dehydration of β-ketoesters to generate conjugated and deconjugated alkynyl esters and conjugated allenyl esters. This sequential one-pot method involves the formation of a vinyl trifl
- Maity, Pradip,Lepore, Salvatore D.
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supporting information; experimental part
p. 158 - 162
(2009/04/07)
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- Reaction of allenyl esters with sodium azide: An efficient synthesis of E-vinyl azides and polysubstituted pyrroles
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(Chemical Equation Presented) The nucleophilic addition of sodium azide to 1,2-allenyl esters can generate vinyl azides in excellent yields with excellent regio- and stereoselectivities. Moreover, pyrroles are synthesized using 1-allyllic 1,2-allenyl este
- Huang, Xian,Shen, Ruwei,Zhang, Tiexin
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p. 1534 - 1537
(2008/04/18)
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- Total synthesis of (±)-hedychenone: Trimethyldecalin terpene systems via stepwise allenoate diene cycloaddition
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(Diagram presented) The total synthesis of hedychenone 1 is described. The cycloaddition of the hindered diene 2 and the allenecarboxylate 3 has been shown conclusively to proceed via the [2+2] cycloadduct 5 to give a 2:1 mixture of the desired formal Diels-Alder adducts, the exo and endo isomers 4xn and is thus a stepwise [4+2] cycloaddition. The exo isomer 4x was converted in four steps (reduction, oxidation, olefination, and desilylation) into hedychenone 1.
- Jung, Michael E.,Murakami, Masayuki
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p. 5857 - 5859
(2007/10/03)
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- Highly efficient [2 + 2] intramolecular cyclizations of allenynes under microwave irradiation: Construction of fused bicyclic compounds
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A palladium [2 + 2] cycloaddition of 1,6- and 1,7- allenyne carboxylates and microwave-mediated [2 + 2] cycloaddition of various 1,n-allenynes were developed and, particularly, the microwave irradiated [2 + 2] cycloaddition of allenynes can provide a simp
- Oh, Chang Ho,Gupta, Arun Kumar,Park, Dai In,Kim, Nakjoong
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p. 5670 - 5672
(2007/10/03)
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- Process for making 2-alkyl-3-hydroxybenzoic acids
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A two step process is described for making 2-alkyl-3-hydroxybenzoic acids or derivatives of benzoic acids by first reacting an allenyl ester or equivalent with furan followed by the ring-opening reaction of the derived bicyclo intermediate with base. The
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- Process for making 2-alkyl-3-hydroxybenzoic acids
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A two step process is described for making 2-alkyl-3-hydroxybenzoic acids or derivatives of benzoic acids by first reacting an allenyl ester or equivalent with furan followed by the ring-opening reaction of the derived bicyclo intermediate with base. The
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- Retro-Ene Reactions in Acylallene Derivatives
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Allenic esters and amides 4 undergo a retro-ene reaction to vinylketene (6) and an aldehyde or imine (5) under the conditions of flash vacuum thermolysis (FVT). The same products are obtained by FVT of cyclobutenones 7 via electrocyclic ring opening to alkoxy- or aminovinylketenes 3 and 1,3-rearrangement of ketenes 3 to allenes 4. All the intermediates and products were characterized by matrix isolation IR spectroscopy, and in the case of 4c the reaction was also monitored by online mass spectrometry. A lower temperature for the retro-ene reaction of 4c, eliminating an imine, than for 4a, eliminating formaldehyde, is in agreement with a lower calculated activation barrier (167 and 181 kJ mol-1, respectively, at the G2(MP2,SVP) level of theory). The allenic amide 11 undergoes an analogous retro-ene reaction to the (unobserved) vinylketene 13, the latter isomerizing to cyclohexenylacrolein 16 in a 1,5-H shift (calculated barrier 125 kJ mol-1; G2 (MP2, SVP)).
- Bibas, Herve,Koch, Rainer,Wentrup, Curt
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p. 2619 - 2626
(2007/10/03)
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- The vinylketene-acylallene rearrangement: Theory and experiment
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Alkoxyviniyketenes 4 are generated by flash vacuum thermolysis (FVT) or photolysis of 3-alkoxycyclobutenones 3. The thermal interconversion of 4 and allene carboxylic acid esters 5 under FVT conditions is demonstrated by Ar matrix FTIR spectroscopy. In addition, ethoxyvinylketene 4b undergoes thermal elimination of ethene with formation of s-cis-and s-trans-acetylketene (8). An analogous aminovinylketene-to-allenecarboxymide conversion is observed on FVT of 3-dimethylaminocyclobutenone 3e. A facile 1,3-chlorine migration in 2,3-butadienoyl chloride (5d) is also reported. Consistent with the experimental observations, 1,3-methoxy, 1,3-chloro, and 1,3-dimethylamino migrations in vinylketene are calculated (G2(MP2,SVP) level) to have moderate barriers of 169, 157, and 129 kJmol-1, respectively, significantly less than the corresponding 1,3-H shift barrier (273 kJ mol-1). The stabilization of the four-center transition structures is rationalized in terms of the donor acceptor interaction between the lone pair electrons of the migrating donor substituent and the vacant central carbon p-orbital of the ketene LUMO. The predicted migratory aptitude in the series of substituted vinylketenes. R-C(=CH2)-CH=C=O, is in the order N(CH3)2>SCH3>SH>Cl>NH2>OCH3>OH>F>H>CH3, and correlates well with the electron-donating ability of the R group.
- Bibas, Herve,Wong, Ming Wah,Wentrup, Curt
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p. 237 - 248
(2007/10/03)
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- β-Methyleneglutamic Acid and β-Methyleneglutamine
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The novel β,γ-unsaturated amino acids β-methyleneglutamic acid (I) and β-methyleneglutamine (II) are readily prepared by addition of the protected aminomalonates III and VIII to the allenes ethyl buta-2,3-dienoate (IV) and cyanoallene (VII) followed by acid hydrolysis.Byproducts of the reaction are 4-amino-3-methylbut-2-enoic acid hydrochloride (VI) and 4-amino-3-methylbut-2-enamide hydrochloride (X).
- Paik, Yi Hyon,Dowd, Paul
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p. 2910 - 2913
(2007/10/02)
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