- A remarkable rate acceleration of the Baylis-Hillman reaction
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Treatment of α-naphthyl acrylate with both aliphatic and aromatic aldehydes in the presence of DABCO (30 mol%) afforded the desired (α-methylene-β-hydroxy)esters with reasonable chemical yields (51-88%) within 20 min.
- Lee,Yang,Chen
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- An Improved Protocol for the Morita-Baylis-Hillman Reaction Allows Unprecedented Broad Synthetic Scope
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The Morita-Baylis-Hillman (MBH) reaction has been stablished as an important C?C bond-forming transformation between carbonyl-containing compounds and activated olefins. However, the slow reaction rate usually observed with electron-rich electrophilic par
- Amarante, Giovanni W.,Camilo, Nilton S.,Carpanez, Arthur G.,Coelho, Fernando,Fernandes, Fábio S.,Lima, Samia R.,Rodrigues, Manoel T.,Santos, Hugo,Serafim, José Cláudio,Silva, Thiago S.,Zeoly, Lucas A.,de Oliveira, Aline S. B.
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supporting information
(2022/01/22)
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- Enantioselective Lewis base catalyzed phosphonyldifluoromethylation of allylic fluorides using a: C -silyl latent pronucleophile
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The first enantioselective phosphonyldifluoromethylation is enabled by the use of diethyl (difluoro(trimethylsilyl)-methyl)phosphonate reagent as a latent pronucleophile in the Lewis base catalyzed substitution of allylic fluorides. The reaction proceeds
- Zi, You,Lange, Markus,Vilotijevic, Ivan
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supporting information
p. 5689 - 5692
(2020/06/19)
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- Unprecedented E-stereoselectivity on the sigmatropic Hurd-Claisen rearrangement of Morita-Baylis-Hillman adducts: A joint experimental-theoretical study
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Herein we report the first systematic investigation of the tandem mercury(ii) catalysed transvinylation/Hurd-Claisen rearrangement of MBH adducts derived from alkyl acrylates. This is the first report of E-selectivity for MBH adducts with alkyl side chain
- Silva, Vinicius Sobral,Tolentino, Terezinha Alves,Rodrigues, Tiago Costa Alves Fontoura,Santos, Fernanda Ferrari Martins,Machado, Daniel Francisco Scalabrini,Silva, Wender Alves,Oliveira, Heibbe Cristhian Benedito De,Machado, Angelo Henrique Lira
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p. 4498 - 4511
(2019/05/17)
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- Organocatalytic Allylic Amination of Morita-Baylis-Hillman Carbonates
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An organocatalytic asymmetric allylic amination of Morita-Baylis-Hillman carbonates with aromatic amines in the presence of β-isocupreidine is described. Chiral allylic amines were obtained in almost quantitative yields (90-96%) with moderate enantioselectivity. Recrystallization afforded products in good yields (45-73%) and high optical purity (82-99% ee). This method provides a facile and efficient route to obtain optically active β-lactams, including the building block of the cholesterol-lowering drug Ezetimibe.
- Formánek, Bed?ich,?imek, Michal,Kamlar, Martin,Císa?ová, Ivana,Vesely, Jan
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p. 907 - 920
(2019/02/10)
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- Direct Synthesis of Dihydropyrrolo[2,1-a]Isoquinolines through FeCl3 Promoted Oxidative Aromatization
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We have developed a straightforward FeCl3 promoted synthesis of dihydropyrrolo[2,1-a]isoquinolines through formal (3+2) cycloaddition/oxidative aromatization cascade of dihydroisoquinoline with Morita-Baylis-Hillman carbonates (up to 96% yield)
- Cui, Hai-Lei,Jiang, Lu,Tan, Hao,Liu, Si
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supporting information
p. 4772 - 4780
(2019/10/28)
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- Decarboxylative Organocatalytic Allylic Amination of Morita–Baylis–Hillman Carbamates
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The present study reports the organocatalytic enantioselective allylic amination of Morita–Baylis–Hillman carbamates efficiently catalyzed by a chiral amine in the presence of a Br?nsted acid. Chiral allylic amines were produced in high yields (up to 98 %) and enantioselectivities (up to 97 % ee). This method provides an efficient and easily performed route to prepare α-methylene-β-lactams, and other optically active β-lactams, such as the cholesterol-lowering drug Ezetimibe.
- Do?ekal, Vojtěch,?imek, Michal,Dra?ínsky, Martin,Vesely, Jan
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supporting information
p. 13441 - 13445
(2018/09/21)
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- Radical Cascade-Triggered Controlled Ring-Opening Polymerization of Macrocyclic Monomers
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A strategy for the controlled radical ring-opening polymerization of macrocyclic monomers is reported. Key to this approach is an allyl alkylsulfone-based ring-opening trigger that can undergo a radical cascade reaction to extrude sulfur dioxide and gener
- Huang, Hanchu,Sun, Bohan,Huang, Yingzi,Niu, Jia
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supporting information
p. 10402 - 10406
(2018/06/27)
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- Synthesis of Chiral α-Trifluoromethylamines with 2,2,2-Trifluoroethylamine as a "building Block"
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The β-isocupreidine, a cinchonine derived alkaloid, catalyzed asymmetric SN2′-SN2′ reaction between N-2,2,2-trifluoroethylisatin ketimines and MBH type carbonates was realized in a simple and efficient way. A series of chiral α-trifl
- Li, Xiaoyuan,Su, Jinhuan,Liu, Zhourujun,Zhu, Yuanyuan,Dong, Zhenghao,Qiu, Shuai,Wang, Jiayi,Lin, Li,Shen, Zhiqiang,Yan, Wenjin,Wang, Kairong,Wang, Rui
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supporting information
p. 956 - 959
(2016/03/15)
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- Versatile O- and S-functionalized 1,2,3-triazoliums: Ionic liquids for the Baylis-Hillman reaction and ligand precursors for stable MIC-transition metal complexes
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The efficient synthesis of O- and S-functionalized 1,2,3-triazoliums is reported. Owing to their physical properties, these cations are efficient ionic liquids for Baylis-Hillman addition under mild reaction conditions. Simultaneously, the functionalizati
- Mendoza-Espinosa, Daniel,González-Olvera, Rodrigo,Osornio, Cecilia,Negrón-Silva, Guillermo E.,Santillan, Rosa
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supporting information
p. 1587 - 1591
(2015/03/18)
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- Synthesis of chiral β2-amino acids by asymmetric hydrogenation
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The synthesis of chiral β2-amino acids by homogeneous asymmetric hydrogenation is discussed. Prochiral β-aryl- or β-hetaryl-α-N-benzyl/N-acetyl/N-Boc substituted α- aminomethylacrylates used as substrates were prepared by a Baylis-Hillman react
- Luehr, Susan,Holz, Jens,Zayas, Odalys,Wendisch, Volkmar,Boerner, Armin
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p. 1301 - 1319
(2012/11/07)
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- Iodine-mediated intramolecular electrophilic aromatic cyclization in allylamines: A general route to synthesis of quinolines, pyrazolo[4,3-b] pyridines, and thieno[3,2-b]pyridines
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An unprecedented synthesis of aromatic ring annulated pyridines from suitably substituted primary allylamines via intramolecular electrophilic aromatic cyclization mediated by molecular iodine under mild conditions is described.
- Batchu, Harikrishna,Bhattacharyya, Soumya,Batra, Sanjay
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supporting information
p. 6330 - 6333
(2013/02/23)
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- α-Sulfonyl succinimides: Versatile sulfinate donors in Fe-catalyzed, salt-free, neutral allylic substitution
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Allyl sulfones are versatile intermediates in organic chemistry. The presence of two distinct functional groups sets the stage for a plethora of subsequent transformations. However, despite these advantages the preparation of regioisomerically enriched sulfones is not easy. The use of sulfinate salts as nucleophiles in substitutions is frequently accompanied by side reactions such as π-bond migration, β-elimination, and so on. Herein we present a preparatively simple way to synthesize a variety of different aryl or alkyl allyl sulfones starting from readily accessible allylic carbonates. By employing aryl or alkyl α-sulfonyl succinimides as sulfinate synthons, mild and regioselective ipso substitution of diverse allylic carbonates was realized.
- Jegelka, Markus,Plietker, Bernd
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supporting information; experimental part
p. 10417 - 10430
(2011/10/31)
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- Asymmetric synthesis of 2-alkyl-3-phosphonopropanoic acid derivatives via Rh-catalyzed asymmetric hydrogenation
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The commercially available ferrocene-based diphosphine ligand (S c,SFc)-TaniaPhos was found to be highly effective in the Rh-catalyzed asymmetric hydrogenation of 3-aryl-2-(phosphonomethyl)propenates. Excellent enantioselectivity (90
- Luo, Li-Bin,Wang, Dao-Yong,Zhou, Xiao-Mao,Zheng, Zhuo,Hu, Xiang-Ping
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experimental part
p. 2117 - 2123
(2012/03/27)
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- Lewis base catalyzed enantioselective allylic hydroxylation of Morita-Baylis-Hillman carbonates with water
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A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using 18O-labeling experiments.
- Zhu, Bo,Yan, Lin,Pan, Yuanhang,Lee, Richmond,Liu, Hongjun,Han, Zhiqiang,Huang, Kuo-Wei,Tan, Choon-Hong,Jiang, Zhiyong
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experimental part
p. 6894 - 6900
(2011/10/09)
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- Enantioselective Rh-catalyzed hydrogenation of 3-aryl- 2phosphonomethylpropenoates by a new class of chiral ferrocenyl diphosphine ligands
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A new class of chiral ferrocenyl diphosphine ligands with an imidazole ring, (Rc,SFc,)-ImiFerroPhos, has been prepared from acylferrocenes through a five-step transformation and successfully applied in the Rh-catalyzed asymmetric hyd
- Wang, Dao-Yong,Hu, Xiang-Ping,Hou, Chuan-Jin,Deng, Jun,Yu, Sai-Bo,Duan, Zheng-Chao,Huang, Jia-Di,Zheng, Zhuo
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supporting information; experimental part
p. 3226 - 3229
(2009/12/09)
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- Asymmetric organocatalysed [1,3]-sigmatropic rearrangements
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The first organocatalysed enantioselective [1,3]-sigmatropic O- to N-rearrangement reactions are presented. The reactions take place under regio- and enantioselective control, and are catalysed by cinchona alkaloids. Two reactions have been developed the first one is the rearrangement of imidates to amides, while the other rear rangement occurs from carbamates to amines via a decarboxylation. Both transformations give nitrogen protected β-amino acid derivatives as the product. These novel asymmetric organocatalysed [1,3]-sigmatropic O- to N-rearrangement reactions provide a reliable and efficient synthetic method for obtaining enantioenriched β-amino acid derivates in good yield from racemic starting materials.
- Kobbelgaard, Sara,Brandes, Sebastian,Jorgensen, Karl Anker
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scheme or table
p. 1464 - 1471
(2009/04/04)
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- A novel ytterbium/perfluoroalkylated-pyridine catalyst for Baylis-Hillman reaction in a fluorous biphasic system
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Ytterbium perfluorooctanesulfonate [Yb(OPf)3] catalyses the highly efficient Baylis-Hillman reaction in the presence of a catalytic amount of a novel perfluoroalkylated-pyridine as a ligand in a fluorous biphasic system (FBS) composed of toluen
- Yi, Wen-Bin,Cai, Chun,Wang, Xin
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p. 919 - 924
(2008/03/14)
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- Asymmetric synthesis of 2-alkyl-3-phosphonopropanoic acids via P - C bond formation and hydrogenation
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Allylic acetates, formed by the acetylation of Baylis Hillman adducts, undergo addition of phosphorus nucleophiles to give stereoselectively the Z-unsaturated esters. TFA cleavage of the fert-butyl ester and asymmetric hydrogenation of the unsaturated aci
- Badkar, Pallavi A.,Rath, Nigam P.,Spilling, Christopher D.
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p. 3619 - 3622
(2008/02/12)
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- Enantioselective allylic substitution of Morita-Baylis-Hillman adducts catalyzed by planar chiral [2.2]paracyclophane monophosphines
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Planar chiral [2,2]cyclophane monophosphines are efficient catalyst in the reaction of Morita-Baylis-Hillman adducts with phthalimide. The corresponding allylic substituted products were afforded in high yields and in good to moderate ee.
- Zhang, Tang-Zhi,Dai, Li-Xin,Hou, Xue-Long
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p. 1990 - 1994
(2008/02/13)
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- Stereoselective iodocyclization of 3-acylamino-2-methylene alkanoates: Synthesis of analogues of N-benzoyl-syn-phenylisoserine
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(Matrix Presented) A convenient approach to racemic analogues of N-benzoyl-syn-phenylisoserine was realized via the stereoselective iodocyclization of amides obtained from Baylis-Hillman adducts.
- Galeazzi, Roberta,Martelli, Gianluca,Mobbili, Giovanna,Orena, Mario,Rinaldi, Samuele
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p. 2571 - 2574
(2007/10/03)
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- Novel application of phosphonium salts as co-catalysts for the Baylis-Hillman reaction
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Excellent yields have been obtained when the Baylis-Hillman reaction is conducted in the presence of phosphonium salts.
- Johnson, Claire L.,Donkor, Rachel E.,Nawaz, Wafaa,Karodia, Nazira
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p. 7359 - 7361
(2007/10/03)
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- One-pot sequential Baylis-Hillman and Michael reactions
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A new one-pot procedure for the sequential Baylis-Hillman and Michael reactions has been developed to construct two carbon-carbon bonds with three components. This procedure has been applied to combine a variety of aromatic aldehydes, β-unsubstituted acry
- Wang, Wengui,Yu, Marvin
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p. 7141 - 7143
(2007/10/03)
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- Rate acceleration of the Baylis-Hillman reaction in polar solvents (water and formamide). Dominant role of hydrogen bonding, not hydrophobic effects, is implicated
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A substantial acceleration of the Baylis-Hillman reaction between cyclohexenone and benzaldehyde has been observed when the reaction is conducted in water. Several different amine catalysts were tested, and as with reactions conducted in the absence of so
- Aggarwal, Varinder K.,Dean, David K.,Mereu, Andrea,Williams, Richard
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p. 510 - 514
(2007/10/03)
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- The Baylis-Hillman reaction under high pressure induced by water-freezing
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High pressure (about 200 MPa), which was realized by freezing water in a sealed autoclave, has been successfully applied to the Baylis-Hillman reaction, in which an efficient rate enhancement was observed.
- Hayashi, Yujiro,Okado, Kotaro,Ashimine, Itaru,Shoji, Mitsuru
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p. 8683 - 8686
(2007/10/03)
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- The Baylis-Hillman reaction: Rate acceleration in silica gel solid phase medium
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Remarkable rate acceleration in the Baylis-Hillman reaction of aromatic aldehydes with acrylates, particularly tertbutyl acrylate, in silica gel solid phase medium has been described.
- Basavaiah,Reddy
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p. 985 - 988
(2007/10/03)
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- Ionic liquids as a recyclable reaction medium for the Baylis-Hillman reaction
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The Baylis-Hillman reaction using 1,4-diazabicyclo[2.2.2]octane (DABCO) has been shown to be 33.6 times faster in the recyclable ionic liquid 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) than in acetonitrile. Low yields (14-2
- Rosa, Jo?o N,Afonso, Carlos A.M,Santos, António G
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p. 4189 - 4193
(2007/10/03)
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- Superior amine catalysts for the Baylis-Hillman reaction: The use of DBU and its implications
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DBU, which is normally regarded as a hindered and non-nucleophilic base, is in fact the optimum catalyst for the Baylis-Hillman reaction, providing adducts at much faster rates than using DABCO or 3HQD; the scope of the Baylis-Hillman reaction is enhanced
- Aggarwal, Varinder K.,Mereu, Andrea
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p. 2311 - 2312
(2007/10/03)
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- Lithium perchlorate-accelerated Baylis-Hillman reactions
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The coupling of α, β-unsaturated carbonyl compounds with aldehydes (the Baylis-Hillman reaction) was accelerated in the presence of a catalytic amount of 1,4-diazabicyclo[2,2,2]octane (DABCO) and lithium perchlorate in ether. A preliminary kinetic study r
- Kawamura, Mikako,Kobayashi, Shu
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p. 1539 - 1542
(2007/10/03)
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- Metal- and ligand-accelerated catalysis of the Baylis-Hillman reaction
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The Baylis-Hillman reaction, the coupling of an unsaturated carbonyl compound/nitrile with aldehydes, is a valuable reaction but is limited in its practicality by poor reaction rates. We have endeavored to accelerate the reaction using Lewis acids and fou
- Aggarwal, Varinder K.,Mereu, Andrea,Tarver, Gary J.,McCague, Ray
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p. 7183 - 7189
(2007/10/03)
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- The 'Baylis - Hillman reaction' mechanism and applications revisited
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It is shown that reaction of aryl, benzyl, alkyl and functionalised alkyl acrylic esters with benzaldehyde, in the presence of 1,4-diazabicyclo[2.2.2] octane, strongly depends upon the electronic and steric effects of the ester part. This influence is also observed in condensation of furfuraldehyde. Moreover, for the first time, it is shown that the overall condensation is equilibrated.
- Fort, Yves,Berthe, Marie Christine,Caubere, Paul
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p. 6371 - 6384
(2007/10/02)
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- Preparation and Selected Reactions of t-Butyl 2-Methylene-3-oxoalkanoates
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The title class of 1,1-diactivated ethylenes has been prepared in two steps from aldehydes and t-butyl acrylate by (i) DABCO-catalyzed coupling to give t-butyl 2-(hydroxyalkyl)-2-propenoates 11 and (ii) low-temperature Jones oxidation, followed by swift work up at low temperature.The resulting butyl 2-methylene-3-oxoalkanoates 12 are stabilized by sterically demanding and also by aromatic groups R.For primary unhindered alkyl groups, stability is low.The compounds enter into Michael reactions, hetero Diels-Alder additions with enol ethers, and self-dimerization.Key Words: Ethylenes, 2,2-diactivated/ Michael acceptors/ 1-Oxa-1,3-butadienes/Hetero Diels-Alder reaction
- Hoffmann, H. Martin R.,Gassner, Andreas,Eggert, Ulrike
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p. 2475 - 2480
(2007/10/02)
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