Silver-catalyzed asymmetric Michael addition of azomethine ylide to arylidene diphosphonates using ThioClickFerrophos ligand

Kimura, Midori; Tada, Atsuo; Tokoro, Yuichiro; Fukuzawa, Shin Ichi

doi:10.1016/j.tetlet.2015.03.024

Cited by 17 publications

(5 citation statements)

References 31 publications

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“…However, for the tert -butyl ester (R = t Bu), the cycloadducts formed as major products without added base (up to 99% yield and 98% ee; Scheme a). The application of this catalyst system was further extended to the reaction of α,β-unsaturated malonates, α-enones, and arylidene diphosphonates, furnishing a range of syn-adducts in high yields with up to 97:3 dr and 99% ee (Scheme , panels c and d). , …”

Section: C–c Bond Formation By Metal-catalyzed Aca Reactionsmentioning

confidence: 99%

“…The application of this catalyst system was further extended to the reaction of α,βunsaturated malonates, α-enones, and arylidene diphosphonates, furnishing a range of syn-adducts in high yields with up to 97:3 dr and 99% ee (Scheme 36, panels c and d). 184,185 The Cu-catalyzed ACA of aromatic nitroalkenes using glycine derivatives as nucleophiles, carried out in the presence of catalysts based on (S,S p )-FOXAP L60a and L60b, was developed by Hou and co-workers. 186 The copper salt Cu(ClO 4 ) 2 was identified as the best metal source for the reaction (72−99% yields, up to 98:2 dr and 86−98% ee's; Scheme 37a).…”

Section: Conjugate Addition Of Aldehydes and Ketonesmentioning

confidence: 99%

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Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles

2018

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The metal-catalyzed asymmetric conjugate addition (ACA) reaction has emerged as a general and powerful approach for the construction of optically active compounds and is among the most significant and useful reactions in synthetic organic chemistry. In recent years, great progress has been made in this area with the use of various chiral metal complexes based on different chiral ligands. This review provides comprehensive and critical information on the enantioselective 1,4-conjugate addition of nonorganometallic (soft) nucleophiles and their importance in synthetic applications. The literature is covered from the last 10 years, and a number of examples from before 2007 are included as background information. The review is divided into multiple parts according to the type of nucleophile involved in the reaction (such as C-, B-, O-, N-, S-, P-, and Si-centered nucleophiles) and metal catalyst systems used.

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Section: C–c Bond Formation By Metal-catalyzed Aca Reactionsmentioning

confidence: 99%

Section: Conjugate Addition Of Aldehydes and Ketonesmentioning

confidence: 99%

Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles

2018

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“…Azomethine ylides are a robust tool for the formation of cyclic nitrogen-containing ring systems that serve as essential yet challenging motifs within natural products and pharmaceuticals . Intra- and intermolecular cyclization occur via dimerization, − Michael-type addition, − and electrocyclization, − but primarily through [3 + 2] cycloaddition with dipolarophiles. − First reported by Huisgen in the early 1960s, − [3 + 2] dipolar cycloadditions are efficient and regioselective methods for forming cyclic compounds, typically following Woodward–Hoffmann rules . Moreover, Houk’s theoretical and computational work into [3 + 2] cycloadditions has established a mechanistic framework for synthetic control. − Strategic use of 1,3-dipolar cycloadditions has been pivotal in the synthesis of several natural products (Figure ), including daphniphyllum 1 , stemofoline 2 , daphnilactone 3 , pancracine 4 , epibatidine 5 , and 5-deoxymubironine 6 .…”

Section: Introductionmentioning

confidence: 99%

Multi-Ion Bridged Pathway of N-Oxides to 1,3-Dipole Dilithium Oxide Complexes

et al. 2021

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Roussi's landmark work on the generation of 1,3dipoles from tertiary amine N-oxides has not reached its full potential since its underlying mechanism is neither well explored nor understood. Two competing mechanisms were previously proposed to explain the transformation involving either an iminium ion or a diradical intermediate. Our investigation has revealed an alternative mechanistic pathway that explains experimental results and provides significant insights to guide the creation of new Noxide reagents beyond tertiary alkylamines for direct synthetic transformations. Truhlar's M06-2x functional and Møller−Plesset second-order perturbation theory with Dunning's [jul,aug]-cc-pv[D,T]z basis sets and discrete-continuum solvation models were employed to determine activation enthalpies and structures. During these mechanistic explorations, we discovered a unique multiion bridged pathway resulting from the rate-determining step, which was energetically more favorable than other alternate mechanisms. This newly proposed mechanism contains no electrophilic intermediates, strengthening the reaction potential by broadening the reagent scope and limiting the possible side reactions. This thoroughly defined general mechanism supports a more direct route for improving the use of N-oxides in generating azomethine ylide−dilithium oxide complexes with expanded functional group tolerance and breadth of chemistry.

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“…The syn adducts 73 were formed as the major diastereomers (Scheme 18). 24 Scheme 13 Ag/Xing-Phos-catalyzed highly diastereoselective addition of aldimino ester to conjugated enones: asymmetric synthesis of pyrrolines…”

Section: Scheme 16 Diastereoselective Synthesis Of Pyrrolidines Via Cmentioning

confidence: 99%

Recent Developments in Highly Stereoselective Michael Addition Reactions Catalyzed by Metal Complexes

Reznikov

Klimochkin²

2020

Synthesis

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Achieving high enantioselectivity and diastereoselectivity simultaneously is a rather challenging task for asymmetric catalytic synthesis. Thanks to the rapid development of asymmetric transition-metal catalysis, significant progress has been made during recent years in achieving highly enantio- and diastereoselective conjugate addition reactions with a diverse combination of Michael donors and acceptors. This short review surveys the advances in transition-metal-catalyzed asymmetric diastereoselective Michael addition including diastereodivergent catalysis developed between 2015 and 2019. The review is divided into multiple parts according to the type of nucleophiles involved in the reaction.1 Introduction2 Addition of Functionalized Ketones and Dicarbonyl Compounds3 Addition of Aldimino Esters and Their Cyclic Analogues4 Addition of Indolin-2-ones5 Vinylogous Michael Reactions6 Other Michael Donors7 Cascade Reactions Initiated by Michael Addition8 Conclusion

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Silver-catalyzed asymmetric Michael addition of azomethine ylide to arylidene diphosphonates using ThioClickFerrophos ligand

Cited by 17 publications

References 31 publications

Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles

Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles

Multi-Ion Bridged Pathway of N-Oxides to 1,3-Dipole Dilithium Oxide Complexes

Recent Developments in Highly Stereoselective Michael Addition Reactions Catalyzed by Metal Complexes

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