- Iron-Catalyzed Aerobic Oxidation and Annulation Reaction of Pyridine and α-Substituted Allenoate toward Functionalized Indolizine
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An iron-catalyzed reaction of pyridine and α-substituted allenoate has been disclosed. The present strategy incorporates the aerobic oxidation into annulation involving substituted allenoate, thus providing a new access to functionalized indolizine.
- Jin, Tao,Tang, Zhongzhong,Hu, Jie,Yuan, Hongdong,Chen, Yaoyao,Li, Chunju,Jia, Xueshun,Li, Jian
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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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- Diastereoselective Synthesis of Tetracyclic Tetrahydroquinoline Derivative Enabled by Multicomponent Reaction of Isocyanide, Allenoate, and 2-Aminochalcone
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We report here a multicomponent protocol to assemble several polycyclic dihydropyran-fused tetrahydroquinoline structures with excellent diastereoselectivity. This procedure employs simple feedstocks to accomplish a series of diverse structures, which is
- Wang, Zhishuang,Fei, Youwen,Tang, Chongrong,Cui, Lei,Shen, Jie,Yin, Kun,Lu, Shanya,Li, Jian
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p. 4094 - 4098
(2021/05/26)
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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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- Carbon-nitrogen bond cleavage of pyridine with two molecular substituted allenoates: Access to 2-arylpyrimidin-4(3: H)-one
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A DABCO-catalyzed annulation reaction of pyridin-2-amine and substituted allenoates has been disclosed. This strategy allows for the ring-opening of a pyridine ring system and the formation of two new rings including a pyrimidinone ring and a benzene ring
- Jin, Tao,Yuan, Hongdong,Su, Shikuan,Jia, Xueshun,Li, Chunju,Li, Jian,Fang, Jianhui
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p. 14128 - 14131
(2019/01/03)
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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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- Unique Reactivity of α-Substituted Electron-Deficient Allenes using Sulfinate Salts as Lewis Base Organocatalysts
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The efficient sulfinate-catalyzed intermolecular addition reaction of α-substituted allenyl sulfones and allenoates with Michael acceptors is highlighted. The sequence proceeds under mild conditions to provide a scalable and efficient access to versatile
- Martzel, Thomas,Lohier, Jean-Fran?ois,Gaumont, Annie-Claude,Brière, Jean-Fran?ois,Perrio, Stéphane
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- Synthesis of Spirobidihydropyrazole through Double 1,3-Dipolar Cycloaddition of Nitrilimines with Allenoates
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The double 1,3-dipolar cycloaddition of allenoates with nitrilimines has been achieved under mild reaction conditions, affording a variety of spirobidihydropyrazoles in moderate to excellent yields with excellent diastereoselectivities. The reaction diastereoselectively constructs double dihydropyrazole moieties and two chiral centers including a spiro carbon center.
- Liu, Honglei,Jia, Hao,Wang, Bo,Xiao, Yumei,Guo, Hongchao
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supporting information
p. 4714 - 4717
(2017/09/23)
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- Phosphine-Catalyzed Enantioselective [4 + 3] Annulation of Allenoates with C,N-Cyclic Azomethine Imines: Synthesis of Quinazoline-Based Tricyclic Heterocycles
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With the use of a commercially available chiral phosphine as the catalyst, the first catalytic enantioselective [4 + 3] annulation of allenoates with C,N-cyclic azomethine imines is developed. The reaction works efficiently under mild reaction conditions to afford seven-membered ring-fused quinazoline-based tricyclic heterocycles in high yields with good to excellent diastereo- and enantioselectivities.
- Yuan, Chunhao,Zhou, Leijie,Xia, Miaoren,Sun, Zhanhu,Wang, Dongqi,Guo, Hongchao
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supporting information
p. 5644 - 5647
(2016/11/17)
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- Synthesis of terminal allenes through copper-mediated cross-coupling of ethyne with N-tosylhydrazones or α-diazoesters
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Ethyne is employed as coupling partner in coppermediated cross-coupling reactions with N-tosylhydrazones and α-diazoacetate, leading to the development of a new synthetic method for terminal allenes. With this novel coupling method, the terminal allenes w
- Ye, Fei,Wang, Chengpeng,Ma, Xiaoshen,Hossain, Mohammad Lokman,Xia, Ying,Zhang, Yan,Wang, Jianbo
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p. 647 - 652
(2016/09/12)
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- Isocyanide-based multicomponent reactions: Concise synthesis of spirocyclic oxindoles with molecular complexity by using a [1,5]-hydrogen shift as the key step
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A concise multicomponent reaction of isocyanide, α-substituted allenoate, and methyleneindolinone has been disclosed. This protocol provides a fast and straightforward approach to synthesize unusual tricyclic oxindoles in an efficient and atom-economic manner. Mechanistically, the present cycloaddition may proceed through a cascade sequence involving double Michael addition, double cyclization, double [1,5]-hydrogen shift, and group migration. The introduction of a special alkyl group to the allenoate is believed to play a key role in the cascade reaction. This method also features a broad substrate scope, which is particularly useful for the delivery of a large number of compounds. Shift your perspective! An unprecedented cascade reaction, under mild conditions, involving a double Michael addition, double cyclization, and double [1,5]-hydrogen shift, followed by group migration is disclosed. This reaction offers a fast and straightforward approach to unusual polycyclic spirooxindoles (see scheme).
- Su, Shikuan,Li, Chunju,Jia, Xueshun,Li, Jian
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p. 5905 - 5909
(2014/05/20)
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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 cascade cycloaddition involving tropone, allenoate, and isocyanide: A rapid access to a 7,6,5-fused tricyclic skeleton
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Multicomponent cascade cycloaddition of tropone, allenoate, and isocyanide has been disclosed. This method allows for the rapid construction of a highly unusual tricyclic skeleton in an efficient manner. The proposed transformation proceeds through [8 + 2 + 1] cycloaddition, [1,5]-H shift, and cyclization followed by an alkoxy group migration process.
- Jia, Shuanglong,Su, Shikuan,Li, Chunju,Jia, Xueshun,Li, Jian
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p. 5604 - 5607
(2015/02/19)
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- Gold-catalyzed simultaneous formation of C-C, C=O, and C-F bonds in the presence of selectfluor: A synthesis of fluoroindenes from allene esters
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An approach for the synthesis of fluorinated indene derivatives has been developed via a gold-catalyzed three-component tandem reaction between allene esters, Selectfluor, and water.
- Liu, Yunkui,Zhu, Jie,Qian, Jianqiang,Xu, Zhenyuan
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p. 5411 - 5417
(2012/08/07)
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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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- Platinum-catalyzed intramolecular hydroarylation of allenyl arenes: Efficient synthesis of 1,4-dihydronaphthalenes
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An efficient synthetic method of 1,4-dihydronaphthalenes having various alkyl groups on the 4-position and/or ethoxycarbonyl group on the 2-position through selective intramolecular Pt-catalyzed 6-endo cyclohydroarylation of ethyl 2-benzyl-2,3-alkadienoat
- Mo, Juntae,Lee, Phil Ho
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supporting information; experimental part
p. 2570 - 2573
(2010/08/22)
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- Small-molecule inhibitors of protein geranylgeranyltransferase type I
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Small molecules that inhibit the geranylgeranylation of K-Ras4B and RhoA by protein geranylgeranyltransferase type I (GGTase-I) were identified from chemical genetic screens of heterocycles synthesized through phosphine catalysis of allenes. To further improve the efficacy of the GGTase-I inhibitors (GGTIs), 4288 related compounds bearing core dihydropyrrole/pyrrolidine and tetrahydropyridine/piperidine scaffolds were synthesized on SynPhase lanterns in a split-pool manner through phosphine-catalyzed [3 + 2] and [4 + 2] annulations of resin-bound allenoates. Testing of the 4288 analogues resulted in several GGTIs exhibiting submicromolar IC50 values. Because proteins such as Ras and Rho GTPases are implicated in oncogenesis and metastasis, these GGTIs might ultimately lead to the development of novel antitumor therapeutics. Copyright
- Castellano, Sabrina,Fiji, Hannah D. G.,Kinderman, Sape S.,Watanabe, Masaru,De Leon, Pablo,Tamanoi, Fuyuhiko,Kwon, Ohyun
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p. 5843 - 5845
(2008/03/14)
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- Reaction of 2,3-allenoates with TsNBr2 in the presence of base: A facile highly stereoselective synthesis of (1E,2E)-3-bromo-4-oxo-N′- tosyl-2-alkenoxylimidic acid ethyl esters
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(Chemical Equation Presented) A novel reaction pathway of 2,3-allenoates with an electrophile (TsNBr2) in the presence of K2CO 3 to produce (1E,2E)-3-bromo-4-oxo-N′-tosyl-2-alkenoxylimidic acid ethyl esters is reported. Th
- Shen, Ruwei,Huang, Xian
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p. 3961 - 3964
(2008/02/01)
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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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- An expedient phosphine-catalyzed [4 + 2] annulation: Synthesis of highly functionalized tetrahydropyridines
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Ethyl 2-methyl-2,3-butadienoate acts as a 1,4-dipole synthon and undergoes [4 + 2] annulation with N-tosylimines in the presence of an organic phosphine catalyst. The resulting adducts, ethyl 6-substituted-1-(4-tosyl)-1,2,5,6-tetrahydro-pyridine-3-carboxylates, are formed in excellent yields with complete regioselectivity. Mechanistic reasoning for this new annulation has led to an expansion of the reaction scope by employing ethyl 2-(substituted-methyl)-2,3-butadienoates to give ethyl 2,6-cis-disubstituted-1-(4-tosyl)-1,2,5,6-tetrahydro-pyridine-3-carboxylates with high diastereoselectivities. Copyright
- Zhu, Xue-Feng,Lan, Jie,Kwon, Ohyun
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p. 4716 - 4717
(2007/10/03)
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- Efficient synthesis of 4-(2′-alkenyl)-2,5-dihydrofurans and 5,6-dihydro-2H-pyrans via the Pd-catalyzed cyclizative coupling reaction of 2,3- or 3,4-allenols with allylic halides
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In the absence of a base, palladium(II) catalysts, such as PdCl2, PdCl2(CH3CN)2, Pd(OAc)2, and [(π-C3H5)PdCl]2, can catalyze the cyclizative coupling reaction of 2,3- or 3,4-allenols with allylic halides in DMA at room temperature to provide 2,5-dihydrofurans and 5,6-dihydro-2H-pyrans, respectively, in moderate to good yields. Under similar reaction conditions, nonsubstituted 2,3-allenol 1s affords bimolecular cyclizative coupling product 5s as the major product. The scope of the reaction and its mechanism have been studied briefly. On the basis of the experimental results, the transformation was believed to proceed via a divalent palladium-catalyzed pathway.
- Ma, Shengming,Gao, Wenzhong
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p. 6104 - 6112
(2007/10/03)
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- Control of regioselectivity in Pd(0)-catalyzed coupling-cyclization reaction of 2-(2′,3′-allenyl)malonates with organic halides
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The regioselectivity in the Pd(0)-catalyzed coupling-cyclization of 2-(2′,3′-allenyl)malonates with organic halides is determined by the steric and electronic effects of both substrates. By deliberate control of the reaction conditions, the regioselectivity of this reaction can be tuned. With conditions A and B, the reaction afforded vinylic cyclopropane derivatives, while with conditions C and D, the reaction afforded cyclopentene derivatives in a highly selective manner. Under similar conditions, 1-alkenyl halides tend to form more three-membered cyclic products. The increased steric hindrance at the 2′-positon of the allene moiety and aryl halides favors the formation of five-membered cyclic products. The regioselectivity of the reaction may be explained by the comparison of the relative stabilities of syn- and anti-type π-allyl palladium intermediates.
- Ma, Shengming,Jiao, Ning,Zhao, Shimin,Hou, Hairong
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p. 2837 - 2847
(2007/10/03)
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