- Indium(III) Chloride-Promoted Intramolecular Addition of Allylstannanes to Alkynes
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In the presence of an equimolar amount of InCl3, 8-tributylstannyl-6-octen-1-ynes (allylstannanes bearing an alkynyl group) were efficiently cyclized to 2-allyl-1-methylenecyclopentanes. In contrast, catalytic use of InCl3 gave 2-all
- Miura, Katsukiyo,Fujisawa, Naoki,Hosomi, Akira
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- Bifunctional Organo/Metal Cooperatively Catalyzed [3 + 2] Annulation of para-Quinone Methides with Vinylcyclopropanes: Approach to Spiro[4.5]deca-6,9-diene-8-ones
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A novel [3 + 2] annulation between para-quinone methides and vinylcyclopropanes for the synthesis of spiro[4.5]deca-6,9-diene-8-ones has been described. The palladium and phosphine-thiourea cooperative catalysis system played an important role in high yields and diastereoselectivities. The reaction exhibited good functional group tolerance and scalability.
- Yuan, Zhenbo,Wei, Weiwei,Lin, Aijun,Yao, Hequan
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- Palladium-catalyzed diastereo- And enantioselective [3 + 2] cycloaddition of vinylcyclopropanes with azadienes: Efficient access to chiral spirocycles
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Benzofuran-derived azadienes (BDAs) have been widely used as four-atom synthons in transition-metal-mediated cycloaddition reactions, while the exploitation of their reactivity as a two-atom unit to construct spirocycles is still underdeveloped. Herein, we reported the first palladium(0)-catalyzed diastereo- and enantioselective [3 + 2] annulation of vinylcyclopropanes (VCPs) and BDAs. This transformation is featured with a broad substrate scope (31 examples), allowing for facile access to a variety of enantioenriched spirocycles bearing a quaternary stereogenic center in good yields with excellent regio-, diastereo-, and enantioselectivities (up to 93% yield, >20:1 dr, and mostly >99% ee) under mild reaction conditions. Moreover, the spirocyclic products could be efficiently converted to structurally complex tricyclo[8.3.0.01,5]-azatridecane and tricyclo[7.3.0.01,5]-azadodecane skeletons.
- Liu, Kai,Yang, Jianfeng,Li, Xiaoxun
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- Diastereoselective synthesis of tetrahydrofurans via palladium(0)-catalyzed [3 + 2] cycloaddition of vinylcyclopropanes and aldehydes
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(Chemical Equation Presented) Palladium(0)-catalyzed cycloadditions of malonate-derived vinylcyclopropane 1 and aldehydes to afford 2,5-cis disubstituted tetrahydrofuran derivatives are described. Pd loadings as low as 0.5 mol % were effective in catalyzing the transformation with high yields and diastereoselectivities. Electron-poor aldehydes work best, suggesting that a mechanism involving an initial aldol reaction may be operative.
- Parsons, Andrew T.,Campbell, Matthew J.,Johnson, Jeffrey S.
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- Anti-Markovnikov hydroarylation of alkenes via polysulfide anion photocatalysis
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A protocol for anti-Markovnikov hydroarylation of alkenes with aryl halides has been developed using polysulfide anions as photocatalysts in the presence of the Hantzsch ester and water under irradiation with visible light.
- Chiba, Shunsuke,Li, Haoyu,Liu, Yuliang
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supporting information
p. 6264 - 6267
(2021/07/02)
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- (3+2)-Cycloaddition of Donor-Acceptor Cyclopropanes with Thiocyanate: A Facile and Efficient Synthesis of 2-Amino-4,5-dihydrothiophenes
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An easy and efficient route to obtain 2-amino-4,5-dihydrothiophenes is presented. A formal (3+2)-cycloaddition of donor-acceptor cyclopropanes and ammonium thiocyanate catalyzed by Yb(OTf) 3delivers the desired products in good to excellent yields. A broad range of functional groups is tolerated during this process.
- Jacob, Anu,Barkawitz, Philip,Andreev, Ivan A.,Ratmanova, Nina K.,Trushkov, Igor V.,Werz, Daniel B.
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supporting information
p. 901 - 904
(2021/03/17)
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- Accessing dihydro-1,2-oxazine via cloke-wilson-type annulation of cyclopropyl carbonyls: application toward the diastereoselective synthesis of pyrrolo[1,2- b][1,2]oxazine
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A convenient additive-free synthesis of dihydro-4H-1,2-oxazines via a Cloke-Wilson-type ring expansion of the aryl-substituted cyclopropane carbaldehydes with the hydroxylamine salt is introduced. Comparatively less active cyclopropyl ketones also follow a similar protocol if supplemented by catalytic p-toluene sulfonic acid monohydrate. The transformation is performed in an open-to-air flask as it shows negligible sensitivity toward air/moisture. Dihydro-4H-1,2-oxazines when subjected to cycloaddition with the cyclopropane diester afford a trouble-free formulation of the valued hexahydro-2H-pyrrolo[1,2-b][1,2]oxazine derivatives. A cascade one-pot variant of this two-step strategy offers a comparable overall yield of the final product.
- Banerjee, Prabal,Kumar, Pankaj,Kumar, Rakesh
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supporting information
p. 6535 - 6550
(2020/06/09)
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- Pd-Catalyzed Dearomatization of Anthranils with Vinylcyclopropanes by [4+3] Cyclization Reaction
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Dearomatization of anthranils with vinylcyclopropanes (VCPs) by Pd-catalyzed [4+3] cyclization reaction has been realized. In the presence of a catalytic amount of borane as an activator, bridged cyclic products were obtained in good to excellent yields with excellent stereoselectivities. By introducing a chiral PHOX ligand (L5), asymmetric dearomatization reactions of anthranils with vinylcyclopropanes proceeded with excellent enantioselectivity. Borane plays a key role for the reactivity, likely owing to the formation of a borane–anthranil complex which has been confirmed by NMR experiments.
- Cheng, Qiang,Xie, Jia-Hao,Weng, Yue-Cheng,You, Shu-Li
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supporting information
p. 5739 - 5743
(2019/03/26)
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- Photoredox catalysed allylic trifluoromethylation via ring opening of vinyl cyclopropanes using Langlois reagent
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Trifluoromethylation of vinylcyclopropanes (VCPs) has been developed under mild reaction conditions to synthesize allylic trifluoromethylated derivatives with high yield and E/Z selectivity using visible light photo-redox catalysis and Langlois reagent (CF3SO2Na) as a trifluoromethylation source. Further, we demonstrate a gram scale synthesis procedure for a trifluoromethylation of vinylcyclopropane.
- Chandu, Palasetty,Ghosh, Krishna Gopal,Das, Debabrata,Sureshkumar, Devarajulu
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- Palladium-Catalyzed Allylic Alkylation of Aldimine Esters with Vinyl-Cyclopropanes to Yield α,α-Disubstituted α-Amino Acid Derivatives
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A synthetically useful approach for the synthesis of functionalized α, α-disubstituted α-amino acid derivatives via palladium-catalyzed 1,7 addition of readily available aldimine esters to vinylcyclopropanes is reported. This methodology was operated under mild conditions, affording α-allylic α-amino esters in good to excellent yields and excellent regio- and stereoselectivity. This transformation displays broad functional-group tolerance and enantioselective allylic alkylation has also been realized using a chiral phosphine ligand to provide the desired product. (Figure presented.).
- Wang, Jiahua,Dai, Zonghao,Xiong, Cheng,Zhu, Jin,Lu, Jinrong,Zhou, Qingfa
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supporting information
p. 5105 - 5111
(2019/11/11)
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- NaOH-Promoted Chemoselective Cascade Cyclization of Cyclopropyl Esters with Unsaturated Imines: Access to Bioactive Cyclopenta[c]pyridine Derivatives
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A chemoselective cascade cycloaddition reaction is developed for green and efficient access to cyclopenta[c]pyridine derivatives. Simple and inexpensive NaOH is used as the sole catalyst for this process. The δ-carbon of cyclopropyl ester is activated as a nucleophilic carbon to initiate highly chemoselective cascade reactions. Cyclopenta[c]pyridines bearing various substituents are afforded in excellent yields. Preliminary studies on the bioactivities of the afforded products show promising antibacterial activities for potential applications in plant protections.
- Pan, Dingwu,Mou, Chengli,Zan, Ningning,Lv, Ya,Song, Bao-An,Chi, Yonggui Robin,Jin, Zhichao
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supporting information
p. 6624 - 6627
(2019/09/07)
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- An Expeditious Route to trans-Configured Tetrahydrothiophenes Enabled by Fe(OTf)3-Catalyzed [3+2] Cycloaddition of Donor–Acceptor Cyclopropanes with Thionoesters
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A synthetic route to trans-configured tetrahydrothiophenes (THTs) through Fe(OTf)3-promoted [3+2] cycloaddition of donor–acceptor cyclopropanes with thionoesters was developed. The cycloaddition proceeded in high yield with high diastereoselectivity, affording transient α-alkoxy THTs. Not only aromatic and aliphatic thionoesters, but also thionolactone were applicable to the present iron catalysis. Further transformation of the S,O-ketal functionality of the product was achieved in a highly trans diastereoselective manner. Moreover, the utility of our methodology was clearly demonstrated by the synthesis of enantioenriched trans-configured THTs.
- Matsumoto, Yohei,Nakatake, Daiki,Yazaki, Ryo,Ohshima, Takashi
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supporting information
p. 6062 - 6066
(2018/03/28)
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- Cascade One-Pot Synthesis of Indanone-Fused Cyclopentanes from the Reaction of Donor-Acceptor Cyclopropanes and Enynals via a Sequential Hydrolysis/Knoevenagel Condensation/[3+2] Cycloaddition
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A cascade reaction of donor-acceptor cyclopropanes with enynals to construct indanone-fused cyclopentanes via a sequential hydrolysis/Knoevenagel condensation/[3+2] cycloaddition is reported. The desired indanone-fused cyclopentanes were obtained in good yields. This method features mild reaction conditions and broad substrate scope, which render it very appealing to chemists for the synthesis of complex molecules containing an indanone-fused cyclopentane moiety. Moreover, the products could be further converted into compounds with different functional groups through the well-known transformations. (Figure presented.).
- Zhang, Jiantao,Jiang, Huanfeng,Zhu, Shifa
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supporting information
p. 2924 - 2930
(2017/09/08)
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- Lewis Acid Catalyzed Diastereoselective Cycloaddition Reactions of Donor-Acceptor Cyclopropanes and Vinyl Azides: Synthesis of Functionalized Azidocyclopentane and Tetrahydropyridine Derivatives
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Lewis acid catalyzed [3 + 2]-cycloaddition reaction of donor-acceptor cyclopropanes with vinyl azides has been developed to obtain diastereomerically enriched azidocyclopentane derivatives. In addition, thermal chemoselective ring expansion of azidocyclopentanes to tetrahydropyridine derivatives and further diastereospecific reduction to a substituted piperidine derivative, with an excellent yield, was also achieved.
- Dey, Raghunath,Banerjee, Prabal
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supporting information
p. 304 - 307
(2017/04/21)
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- Construction of Isoxazolidines through Formal [3+2] Cycloaddition Reactions of in situ Generated Nitrosocarbonyls with Donor–Acceptor Cyclopropanes: Synthesis of α-Amino γ-Butyrolactones
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A straightforward approach for the synthesis of isoxazolidines through MgI2-catalyzed [3+2] cycloaddition reactions of donor–acceptor cyclopropanes with in situ generated nitrosocarbonyls from hydroxycarbamates is described. This method facilit
- Varshnaya, Rohit Kumar,Banerjee, Prabal
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p. 4059 - 4066
(2016/08/24)
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- Highly functionalized donor-acceptor cyclopropanes applied toward the synthesis of the Melodinus alkaloids
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Abstract A series of highly substituted vinylcyclopropanes were prepared and examined as reaction partners in a palladium-catalyzed (3+2) cycloaddition with nitrostyrenes. Described herein are our efforts to synthesize an elusive 1,1-divinylcyclopropane by several distinct approaches, and to apply surrogates of this fragment toward the synthesis of the Melodinus alkaloids.
- Goldberg, Alexander F.G.,Craig, Robert A.,O'Connor, Nicholas R.,Stoltz, Brian M.
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p. 2983 - 2990
(2015/05/27)
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- Tetrahydro-1,3-oxazepines via Intramolecular Amination of Cyclopropylmethyl Cation
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An efficient synthesis of tetrahydro-1,3-oxazepines was developed involving the regioselective intramolecular amination of cyclopropylmethyl cation. The cation was generated by the abstraction of one imidate group in bis-imidate bearing a carbocation-stabilizing substituent. Using 1,1,2,3-tetrasubstituted cyclopropane substrates, highly diastereoselective intramolecular amination to trans-tetrahydro-1,3-oxazepines was achieved. The resulting tetrahydro-1,3-oxazepines were transformed to the homoallylamine derivatives in high yields.
- Skvorcova, Marija,Grigorjeva, Liene,Jirgensons, Aigars
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supporting information
p. 2902 - 2904
(2015/06/30)
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- Rhodium(iii)-catalyzed C-H/C-C activation sequence: Vinylcyclopropanes as versatile synthons in direct C-H allylation reactions
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Succession of C-H activation and C-C activation was achieved by using a single rhodium(iii) catalyst. Vinylcyclopropanes were used as versatile coupling partners. Mechanistic studies suggest that the olefin insertion step is rate-determining and a facile β-carbon elimination is involved, which represents a novel ring opening mode of vinylcyclopropanes. This journal is
- Wu, Jia-Qiang,Qiu, Zhi-Ping,Zhang, Shang-Shi,Liu, Jing-Gong,Lao, Ye-Xing,Gu, Lian-Quan,Huang, Zhi-Shu,Li, Juan,Wang, Honggen
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supporting information
p. 77 - 80
(2015/01/09)
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- Diastereo- and enantioselective construction of oxindole-fused spirotetrahydrofuran scaffolds through palladium-catalyzed asymmetric [3+2] cycloaddition of vinyl cyclopropanes and isatins
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A novel asymmetric formal [3+2] cycloaddition of vinyl cyclopropanes and isatins in the presence of Pd2(dba)3 and the chiral imidazoline-phosphine ligand (aS,R,R)-L3 has been developed, affording the corresponding highly functionalized oxindole-fused spirotetrahydrofuran frameworks in good yields along with good diastereo- and high enantioselectivities under mild conditions.
- Mei, Liang-Yong,Wei, Yin,Xu, Qin,Shi, Min
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supporting information
p. 3544 - 3556
(2013/07/26)
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- Fe-catalyzed allylic C-C-bond activation: Vinylcyclopropanes as versatile a1,a3,d5-synthons in traceless allylic substitutions and [3 + 2]-cycloadditions
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The low-valent iron complex Bu4N[Fe(CO)3(NO)] (TBAFe) catalyzes the allylic C-C-bond activation of electron-poor vinyl cyclopropanes to generate synthetically useful a1,a3,d5-synthons which are prone to undergo multiple consecutive reactions. The versatility of this approach is demonstrated by a traceless allylic substitution and a formal [3 + 2] cycloaddition to give either functionalized acyclic products or densely substituted cyclopentanes and pyrrolidines in high yields and regioselectivities.
- Dieskau, Andre P.,Holzwarth, Michael S.,Plietker, Bernd
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supporting information; experimental part
p. 5048 - 5051
(2012/05/05)
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- Lewis acid mediated (3 + 2) cycloadditions of donor-acceptor cyclopropanes with heterocumulenes
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Isocyanates, isothiocyanates, and carbodiimides are effective substrates in (3 + 2) cycloadditions with donor-acceptor cyclopropanes for the synthesis of five-membered heterocycles. These reactions exhibit a broad substrate scope, high yields, and well-defined chemoselectivity. Discussed herein are the implications of Lewis acid choice on the stereochemical outcome and the reaction mechanism.
- Goldberg, Alexander F. G.,O'Connor, Nicholas R.,Craig, Robert A.,Stoltz, Brian M.
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supporting information
p. 5314 - 5317,4
(2012/12/12)
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- Lewis acid mediated (3 + 2) cycloadditions of donor-acceptor cyclopropanes with heterocumulenes
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Isocyanates, isothiocyanates, and carbodiimides are effective substrates in (3 + 2) cycloadditions with donor-acceptor cyclopropanes for the synthesis of five-membered heterocycles. These reactions exhibit a broad substrate scope, high yields, and well-defined chemoselectivity. Discussed herein are the implications of Lewis acid choice on the stereochemical outcome and the reaction mechanism.
- Goldberg, Alexander F. G.,O'Connor, Nicholas R.,Craig, Robert A.,Stoltz, Brian M.
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supporting information
p. 5314 - 5317
(2013/01/15)
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- Synthesis of methyl-1-(tert -butoxycarbonylamino)-2- vinylcyclopropanecarboxylate via a hofmann rearrangement utilizing trichloroisocyanuric acid as an oxidant
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A trichloroisocyanuric acid (TCCA) mediated Hofmann rearrangement was utilized to synthesize methyl-1-(tert-butoxycarbonylamino)-2- vinylcyclopropanecarboxylate. A variety of functional groups are tolerated in this reaction including vinyl, cyclopropyl, pyridyl, aryl, benzyl, and nitro groups.
- Crane, Zackary D.,Nichols, Paul J.,Sammakia, Tarek,Stengel, Peter J.
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supporting information; experimental part
p. 277 - 280
(2011/03/20)
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- Cycloadditions of aromatic azomethine imines with 1,1-cyclopropane Diesters
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The cycloaddition of aromatic azomethine imines to 1,1-cyclopropane diesters was achieved using Ni(CIO4)2 as catalyst. The methodology gives access to unique tricyclic dihydroquinoline derivatives with dr up to 6.6:1. A nonconcerted
- Perreault, Christian,Goudreau, Sbastien R.,Zimmer, Lucie E.,Charette, Andr B.
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supporting information; experimental part
p. 689 - 692
(2009/04/06)
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- A PROCESS FOR RESOLVING RACEMIC MIXTURES AND A DIASTEREOISOMERIC COMPLEX OF A RESOLVING AGENT AND AN ENANTIOMER OF INTEREST
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A process for resolving a compound in racemic form comprising the following steps is described: a) reacting a compound in racemic form with a resolving agent, b) forming a diastereoisomeric complex of the resolving agent and an enantiomer of interest, c} separating the enantiomer of interest from the obtained diastereoisomer, wherein such a process is characterized in that said resolving agent is a compound of Formula (I). A diastereoisomeric complex between the resolving agent of Formula (I) and the enantiomer of interest is also described. The process according to the invention allows acid and basic racemic mixtures to be separated.
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Page/Page column 76
(2008/06/13)
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- Indium(III) salt promoted intramolecular addition of allylsilanes to unactivated alkynes
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In the presence of a stoichiometric or catalytic amount of a Lewis acidic indium(III) salt, allylsilanes reacted intramolecularly with unactivated terminal alkynes to give cyclized products in good to high yields. The fact that the reaction proceeded in a
- Miura, Katsukiyo,Fujisawa, Naoki,Toyohara, Sayaka,Hosomi, Akira
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p. 1883 - 1886
(2008/02/08)
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- Intramolecular carbostannylation of allyl- and vinylstannanes via a radical chain process
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In the presence of Bu3SnH and AIBN, 8-tributylstannyl-6-octen-1-ynes were efficiently cyclized to 2-allyl-1-(tributylstannylmethylene)cyclopentanes by intramolecular homolytic allylstannylation. 8-Tributylstannyl-1,6-octadienes as well underwen
- Miura, Katsukiyo,Fujisawa, Naoki,Saito, Hiroshi,Nishikori, Hisashi,Hosomi, Akira
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- CARBANION-INDUCED INTRAMOLECULAR BETA-CLEAVAGE REACTIONS OF 2-OXETANONES
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Intramolecular β-cleavage reactions of β-lactones, or 2-oxetanones, by stabilized enolates have been demonstrated.There-, four-, five-, and six-membered carbocyclic rings have been prepared.
- Mead, Keith T.,Lu, Jinqi
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p. 8947 - 8950
(2007/10/02)
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- Enantioselective synthesis of (1R,2S) and (1S,2S) dehydrocoronamic acids
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Thanks to the successive use of two esterases with different regioselectivities and conventional organic chemistry we have synthesized (1R,2S) and (1S,2S) dehydrocoronamic acids.
- Fliche,Braun,Le Goffic
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p. 2873 - 2876
(2007/10/02)
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- Deprotonation of the adducts of β-dicarbonyl anions and [(η4-diene)Co(CO)3]BF4
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The adducts of stabilized enolates and [(η4-1,3-butadiene)Co(CO)3]BF4 (1) and [(η4-1,3-cyclohexadiene)Co(CO)3]BF4 (2) undergo deprotonation and subsequent reactions to form either hydrofurans, cyclopropanes, or α,β,γ,δ-diunsaturated dicarbonyl derivatives depending upon the reacting complex and the β-dicarbonyl component. All of the observed reactions are strongly promoted by HMPA.
- Barinelli, Lucio S.,Li, Zhong,Nicholas, Kenneth M.
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p. 2474 - 2476
(2008/10/08)
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- Regioselective and Stereoselective Nucleophilic Addition to Electrophilic Vinylcyclopropanes
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Palladium(0) complexes catalyze ring opening of 1,1-diactivated 2-vinylcyclopropanes 2 with concomitant addition of a carbon nucleophile.The reaction is extremely regioselective and stereoselective in that the alkylation occurs syn to the cyclopropane bond being cleaved in bicyclic system (n = 3, 4).
- Burgess, Kevin
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p. 2046 - 2051
(2007/10/02)
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- Process for the preparation of dialkyl 2-vinylcyclopropane-1,1-dicarboxylates
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This invention relates to the preparation of dialkyl-2-vinylcyclopropane-1,1-dicarboxylates involving the addition of an alcoholic metallic alkoxide to an organic solution of a 1,4-dihalobutene-2 and a malonic ester.
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- SYNTHESIS OF CYCLOPROPANES AND 1,4-DISUBSTITUTED trans-2-BUTENES BY OXIDATIVE ADDITIONS OF CARBONYL COMPOUNDS TO 1,3-BUTADIENE PROMOTED BY CERIUM(IV) AMMONIUM NITRATE
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In this paper are reported some oxidative additions of carbonyl compounds to 1,3-butadiene, promoted by cerium(IV) ammonium nitrate, followed by the reaction of the formed 1,2 and 1,4 nitrate adducts with nucleophilic or basic species.Cyclopropane derivat
- Baciocchi, Enrico,Ruzziconi, Renzo
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p. 671 - 676
(2007/10/02)
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- Palladium-Catalyzed Cycloaddition Reaction of Vinylcyclopropanes with α,β-Unsaturated Esters or Ketones
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Reaction of vinylcyclopropanes having two electron-withdrawing groups with α,β-unsaturated esters or ketones in the presence of Pd2(dba)3*CHCl3-1,2-bis(diphenylphosphino)ethane (dppe) or tributylphosphine catalyst gave vinylcyclopentanes in good yields.
- Shimizu, Isao,Ohashi, Yukihiro,Tsuji, Jiro
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p. 3825 - 3828
(2007/10/02)
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- CONJUGATE NUCLEOFHILIC RING OPENING OF ACTIVATED VINYLCYCLOPROPANES FACILITATED BY HOMOGENOUS PALLADIUM CATALYSIS
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1,1-Diactivated-2-vinylcyclopropanes (1) add carbon nucleophiles (2) regiospecifically in a conjugate sense in the presence of a catalytic amount of a zerovalent palladium complex.
- Burgess, Kevin
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p. 3049 - 3052
(2007/10/02)
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- NEW SYNTHETIC METHOD OF (Z)-4-ALKENOIC ACIDS USING RING-OPENING REACTION OF (Z)-4-HEXENOLIDE WITH ORGANOCOPPER REAGENT
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(Z)-4-Hexenolide reacted regioselectively with diorganocuprates to give (Z)-4-alkenoic acids in high yields.Synthetic utility was demonstrated by the convenient synthesis of cis-jasmone.
- Fujisawa, Tamotsu,Umezu, Kazuto,Kawashima, Masatoshi
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p. 1795 - 1798
(2007/10/02)
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- 2-Vinyl- and 2-ethylcyclopropane carboxylates
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Novel 2-vinyl- and 2-ethylcyclopropane carboxylates useful as pesticides, herbicides and chemical intermediates are provided. The products of this invention contain two gem carboxylate STR1 groups, which can be the same or different. The carboxylate groups will contain an aliphatic, cycloaliphatic, aromatic, heteroalkyl or heterocyclic moiety.
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