Combining <i>in situ</i> Generated Chiral Silicon Lewis Acid and Chiral Brønsted Acid Catalysts for [3+2] Cycloadditions: Cooperative Catalysis as a Convenient Enantioselective Route to Pyrazolidines

Serdyuk, Olga V.; Zamfir, Alexandru; Hampel, Frank; Tsogoeva, Svetlana B.

doi:10.1002/adsc.201200293

Cited by 28 publications

(17 citation statements)

References 37 publications

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“…In addition to the above-described silicon Lewis acid-promoted [3+2] cycloadditions of acylhydrazones, Tsogoeva et al [ 35 ] developed a catalytic system comprised of chiral Brønsted acid (chiral BINOL phosphates) and silicon Lewis acid (R 2 SiX 2 ). The combination of both acids acted cooperatively in the stereoselective intermolecular cycloaddition of acylhydrazones with cyclopentadiene providing a convenient and facile process for the synthesis of pyrazolidines.…”

Section: Synthesis Of Pyrazolidinesmentioning

confidence: 99%

Synthesis of Non-Racemic Pyrazolines and Pyrazolidines by [3+2] Cycloadditions of Azomethine Imines

et al. 2017

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Asymmetric [3+2] cycloadditions of azomethine imines comprise a useful synthetic tool for the construction of pyrazole derivatives with a variable degree of saturation and up to three stereogenic centers. As analogues of pyrrolidines and imidazolidines that are abundant among natural products, pyrazoline and pyrazolidine derivatives represent attractive synthetic targets due to their extensive applications in the chemical and medicinal industries. Following the increased understanding of the mechanistic aspect of metal-catalyzed and organocatalyzed [3+2] cycloadditions of 1,3-dipoles gained over recent years, significant strides have been taken to design and develop new protocols that proceed efficiently under mild synthetic conditions and duly benefit from superior functional group tolerance and selectivity. In this review, we represent the current state of the art in this field and detailed methods for the synthesis of non-racemic pyrazolines and pyrazolidines via [3+2] metal and organocatalyzed transformations reported since the seminal work of Kobayashi et al. and Fu et al. in 2002 and 2003 up to the end of year 2017.

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Section: Synthesis Of Pyrazolidinesmentioning

confidence: 99%

Synthesis of Non-Racemic Pyrazolines and Pyrazolidines by [3+2] Cycloadditions of Azomethine Imines

et al. 2017

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“…In 2005, Leighton discovered that chiral pseudoephedrine‐derived silane Lewis acids are efficient promoters (1.5 equiv required) for the 1,3‐DCs between N ‐acylhydrazones and enol ethers . Following this metal‐free activation concept, Tsogoeva and co‐workers reported in 2012 an alternative organocatalytic system for similar reactions between N ‐acylhydrazones 80 and cyclopentadiene 81 (Scheme ) . The use of phosphoric acid ( S )‐ XVIb as the catalyst and Ph 2 SiCl 2 as the Lewis acid led to pyrazolidines 82 in moderate to good yields and, in general, good stereocontrol…”

Section: Hydrazones In Cycloaddition and Other Cyclization Reactionsmentioning

confidence: 99%

Hydrazones as Singular Reagents in Asymmetric Organocatalysis

Retamosa

Matador

Monge

et al. 2016

Chemistry A European J

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This Minireview summarizes strategies and developments regarding the use of hydrazones as reagents in asymmetric organocatalysis, their distinct roles in nucleophileelectrophile reactions, cycloadditions and cyclizations. The key structural elements governing the reactivity of these reagents in a preferred pathway will be discussed, as well as their different interactions with organocatalysts, leading to diverse activation modes. Along these studies, the synthetic equivalence of Nmonoalkyl-, N,N-dialkyl-and N-acyl hydrazones with several synthons is also highlighted. Emphasis is also put on the mechanistic studies performed to understand the observed reactivities. Finally, the functional group transformations performed from the available products has also been analysed, highlighting the synthetic value of these methodologies, which served to access numerous families of valuable multifunctional compounds and nitrogen-containing heterocycles.

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“…As such, BINOL-phosphate catalyzed [3+2] cycloadditions have been introduced as a convenient direct method for the synthesis of pyrazolidine heterocycles [12,13,14], which are ubiquitous in pharmaceutical compounds with antitumor, antimicrobial, anticonvulsant and other biological activities.…”

Section: Cycloadditions Catalyzed By Chiral Binol-derived Phosphormentioning

confidence: 99%

“…Therefore, in 2012 the Tsogoeva group further reported an enantioselective [3+2] cycloaddition as a convenient method towards chiral pyrazolidines in good yields and with high levels of dia- and enantioselectivities, utilizing a cooperative catalytic system of BINOL-derived phosphoric acid 2 and an in situ generated BINOL-phosphate-derived silicon Lewis acid (Scheme 3, Figure 3) [13].…”

Section: Cycloadditions Catalyzed By Chiral Binol-derived Phosphormentioning

confidence: 99%

Enantioselective Cycloaddition Reactions Catalyzed by BINOL-Derived Phosphoric Acids and N-Triflyl Phosphoramides: Recent Advances

2015

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Over the last several years there has been a huge increase in the development and applications of new efficient organocatalysts for enantioselective pericyclic reactions, which represent one of the most powerful types of organic transformations. Among these processes are cycloaddition reactions (e.g., [3+2]; formal [3+3]; [4+2]; vinylogous [4+2] and 1,3-dipolar cycloadditions), which belong to the most utilized reactions in organic synthesis of complex nitrogen-and oxygen-containing heterocyclic molecules. This review presents the breakthrough realized in this field using chiral BINOL-derived phosphoric acids and N-triflyl phosphoramide organocatalysts.

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Combining in situ Generated Chiral Silicon Lewis Acid and Chiral Brønsted Acid Catalysts for [3+2] Cycloadditions: Cooperative Catalysis as a Convenient Enantioselective Route to Pyrazolidines

Abstract: A facile enantioselective synthesis of chiral pyrazolidines via a [3+ 2] cycloaddition reaction, involving a BINOL-derived phosphoric acid and an in situ generated BINOL phosphate-derived silicon Lewis acid, which may act cooperatively, has been developed.

Cited by 28 publications

References 37 publications

Synthesis of Non-Racemic Pyrazolines and Pyrazolidines by [3+2] Cycloadditions of Azomethine Imines

Synthesis of Non-Racemic Pyrazolines and Pyrazolidines by [3+2] Cycloadditions of Azomethine Imines

Hydrazones as Singular Reagents in Asymmetric Organocatalysis

Enantioselective Cycloaddition Reactions Catalyzed by BINOL-Derived Phosphoric Acids and N-Triflyl Phosphoramides: Recent Advances

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