Direct Catalytic Asymmetric Synthesis of Pyrazolidine Derivatives

Deiana, Luca; Zhao, Gui‐Ling; Leijonmarck, Hans; Sun, Junliang; Lehmann, Christian W.; Córdova, Armando

doi:10.1002/open.201200015

Cited by 13 publications

(5 citation statements)

References 79 publications

(23 reference statements)

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“…Cordova and co‐workers also reported a similar asymmetric domino aza‐Michael/hemiaminalization reaction for the synthesis chiral pyrazolidine derivatives 53 (Scheme ) …”

Section: Primary and Secondary Amine Catalystsmentioning

confidence: 93%

“…[45] Cordova andc o-workers also reported as imilar asymmetric domino aza-Michael/hemiaminalization reactionf or the synthesis chiral pyrazolidine derivatives 53 (Scheme15). [46] Very recently,C hen and co-workers utilized 1,2-diaza-1,3-dienes 55 and b-substituted 2-butenals 56 as the reactionp artners in ad omino asymmetric vinylogous 1,6-Michaela ddition/1,4-proton shift/aza-Michael addition/hemiaminal formationr eaction (Scheme 16). [47] Thed ienamine catalysis using the chiral prolinol O-triphenylsilyl ether( S)-59 as the catalyst and 3,5-difluoromandelic acid (60)a sa na cid additive (the same stereoselectivity waso btained with both chiral andr acemic 60)p rovided the bicyclic l,8-diazabicyclo[3.3.0]octane skeletons 58 in high stereo-, regio-andchemoselectivities.…”

Section: 211synthesis Of Aza-heterocyclesmentioning

confidence: 99%

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Recent Progress in Organocatalytic Asymmetric Domino Transformations

2017

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Sustainability in chemical synthesis is a major aspect of the current synthetic endeavors and, therefore,m imicking the biological process in the laboratory nowadays has the highest priority.T owards achieving this goal, designingorganic reactions in domino mode rathert han the multistep synthetic pathways andu sing organocatalysisi nstead of metal catalysis have received al ot of attention due to the inherenta dvantageso ft hese processes in terms of synthetic efficiencya nd sustainability.A saresult, the field of asymmetric organocatalytic domino reactions has witnessed tremendous progress in recent years.T his review attempts to summarize the latest developments in asymmetric organocatalyzed domino reactions since 2012, with the emphasis on the catalysts andr eactionm odes.D iscussions on the reactionm echanismsa nd the applications of the developed domino reactionm ethodsi nt he synthesis of biologically active molecules and natural products are also includedwhen appropriate.

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“…Cordova and co‐workers also reported a similar asymmetric domino aza‐Michael/hemiaminalization reaction for the synthesis chiral pyrazolidine derivatives 53 (Scheme ) …”

Section: Primary and Secondary Amine Catalystsmentioning

confidence: 93%

Section: 211synthesis Of Aza-heterocyclesmentioning

confidence: 99%

Recent Progress in Organocatalytic Asymmetric Domino Transformations

2017

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“…Pyrazolines and pyrazolidines both represent intermediates in the synthesis of pyrazoles and important building blocks for the diversification of in‐demand pharmaceutically active compounds . One facile routes pyrazolines is the 1,3‐dipolar cycloaddition of diazoalkanes with various dipolarophiles.…”

Section: Pyrazoles Pyrazolines and Pyrazolidinesmentioning

confidence: 99%

“…Shortly thereafter, Córdova and co‐workers carried out the reaction shown in Scheme , but with the participation of β‐arylsubstituted enals . This one‐step reaction (11 examples) proceeded in 98–99 % ee and 45–77 % yields.…”

Section: Pyrazoles Pyrazolines and Pyrazolidinesmentioning

confidence: 99%

Synthesis of Diheteroatomic Five‐Membered Heterocyclic Compounds from α,β‐Unsaturated Aldehydes

Keiko

Вчисло

2016

Asian J Org Chem

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The recent increasei ni nterest in the chemistry of azoles has been owing to their paramount importance in several essential fields of research, such as pharmacology, medicine, biology, the organic synthesis of fine chemicals, agriculturalc hemistry, and the chemical industry.T his Focus Review summarizes and highlights recently developed methods for the synthesis of five-membered N,N-, N,O-, andN ,Sheterocycles based on the transformations of 2-alkenals. Over the last 15 years, these reactions, which often differ from reactions involving other a,b-unsaturatedc arbonyl compoundsi nt erms of methoda nd results, have gathered significant momentum. The multitude of catalytic and tech-nological novelties discussed in this Focus Review,s uch as asymmetricm etal-and organocatalysis,o ne-pot multicomponent reactions that proceed through domino, cascade, or tandem sequences, and microwave activation,p romote the formation of ad iverse range of target products, the structures of which becomec lear from the mechanistic schemes given in this Focus Review.T he mechanisms discussed reflect great advances in the chemo-, regio-, and stereoselectivity of the reactions of 2-alkenals, which allows new azoles and related compounds (imidazoles, pyrazoles, oxazoles, thiazoles, and their hydrogenatedd erivatives) to be synthesized.[a] Prof.The ORCID identification number(s) for the author(s) of this articlecan be found under http://dx.Scheme2.One-potsynthesis of imidazoles 8 and tentativemechanism of the reaction.T s= 4-toluenesulfonyl, TMS = tert-butyltrimethylsilyl, Bn = benzyl, Lg = leaving group.Scheme3.Enantioselective synthesiso f3-hydroxyalkyl and 3-aminoalkyli midazo[1,2-a]pyridines (9)through an asymmetricorganocatalytic [3+ +2] annulation strategy.Alk = alkyl.Scheme4.One-potsynthesis of imidazole-containingc ondensed heterocycles by the reaction of 2-alkoxypropenalswith N-binucleophiles.Scheme9.Aroute to 2-(1'-alkoxyvinyl)imidazolidines 27 through the condensation of alkoxy propenals.

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“…[ 1–13 ] Therefore, many experimental and theoretical works have been dedicated to the efficient and stereoselective synthesis of pyrazolidine and pyrazoline compounds. [ 14–28 ] For instance, Kobayashi found that the Lewis acid chiral zirconium/BINOL complex can be used as an efficient catalyst to synthesize entioselectively pyrazolidine products via inter‐ or intra‐molecular [3+2] cycloaddition between hydrazones and alkenes. [ 22–24 ] Müller and List, however, used a chiral Brønsted acid to generate enantiopure pyrazolidine derivative.…”

Section: Introductionmentioning

confidence: 99%

A density functional theory study of the stereoselectivity of Cu(OTf)₂‐catalyzed [3+2] cycloaddition of trifluoromethylated N‐acylhydrazones and isoprene: A concerted asynchronous mechanism

Tang

Wang

et al. 2020

Int J of Quantum Chemistry

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Here we employ density functional theory calculations to systematically investigate the underlying mechanism of Cu(OTf) 2 -catalyzed [3+2] cycloaddition reactions in the synthesis of CF 3 -substituted pyrazolidines. About eight possible initial configurations of the [3+2] reaction is considered, and all relevant reactants, transition states, and products are optimized. Based on these structures, internal reaction coordinate paths, and wavefunction analysis results, we conclude that the Cu(OTf) 2 -catalyzed [3+2] cycloaddition follows a concerted asynchronous mechanism. The C N bond forms immediately after the formation of the C C bond. Among the eight reaction paths, the energy barrier for the [3+2] reaction that leads to the CF 3 -substituted synpyrazolidine is the lowest, $5.4 kcal/mol, which might result in the diastereoselectivity that is observed in the experiment. This work not only gives the detailed mechanism of the Cu(OTf) 2 -catalyzed [3+2] cycloaddition but can also be helpful for the future designation of Cu(OTf) 2 -based cycloaddition processes.

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Direct Catalytic Asymmetric Synthesis of Pyrazolidine Derivatives

Cited by 13 publications

References 79 publications

Recent Progress in Organocatalytic Asymmetric Domino Transformations

Recent Progress in Organocatalytic Asymmetric Domino Transformations

Synthesis of Diheteroatomic Five‐Membered Heterocyclic Compounds from α,β‐Unsaturated Aldehydes

A density functional theory study of the stereoselectivity of Cu(OTf)₂‐catalyzed [3+2] cycloaddition of trifluoromethylated N‐acylhydrazones and isoprene: A concerted asynchronous mechanism

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Direct Catalytic Asymmetric Synthesis of Pyrazolidine Derivatives

Cited by 13 publications

References 79 publications

Recent Progress in Organocatalytic Asymmetric Domino Transformations

Recent Progress in Organocatalytic Asymmetric Domino Transformations

Synthesis of Diheteroatomic Five‐Membered Heterocyclic Compounds from α,β‐Unsaturated Aldehydes

A density functional theory study of the stereoselectivity of Cu(OTf)2‐catalyzed [3+2] cycloaddition of trifluoromethylated N‐acylhydrazones and isoprene: A concerted asynchronous mechanism

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A density functional theory study of the stereoselectivity of Cu(OTf)₂‐catalyzed [3+2] cycloaddition of trifluoromethylated N‐acylhydrazones and isoprene: A concerted asynchronous mechanism