Gold(I)‐Catalyzed Diastereo‐ and Enantioselective Synthesis of Polysubstituted Pyrrolo[3,4‐<i>d</i>][1,2]oxazines

Mei, Zhang; Di, Xiaoyu; Zhang, Mingrui; Zhang, Junliang

doi:10.1002/cjoc.201700575

Cited by 14 publications

(4 citation statements)

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“…Recently, our group reported two novel Au/NHPI/LA ternary catalytic systems by employing t BuONO as a radical source to access multifunctional oxazoles from N -propargylamides (Scheme b) . As our part of continuous interest in radical chemistry as well as gold catalysis, we focused on internal N -propargylamides; to the best of our knowledge, merging gold catalysis and radical chemistry had never been applied to internal N -propargylamides yet. In this context, we envisioned that internal N -propargylamides could smoothly afford vinyl–gold intermediates in the presence of a gold catalyst, which then was attacked by a radical source and afforded 5-oxazole ketone derivatives with TBN as a radical source (Scheme c).…”

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confidence: 99%

Gold-Catalyzed Radical-Involved Intramolecular Cyclization of Internal N-Propargylamides for the Construction of 5-Oxazole Ketones

Mai

Xuan

et al. 2018

J. Org. Chem.

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An expedient strategy for the synthesis of 5-oxazole ketones was developed via homogeneous gold catalysis with 4-MeO-TEMPO as an oxidant. The desired 5-oxazole ketones were achieved in decent yields with an excellent functional group compatibility under mild conditions. The current protocol also represents the first example for merging a gold catalyst and radical chemistry in one-pot synthesis with internal N-propargylamides.

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confidence: 99%

Gold-Catalyzed Radical-Involved Intramolecular Cyclization of Internal N-Propargylamides for the Construction of 5-Oxazole Ketones

Mai

Xuan

et al. 2018

J. Org. Chem.

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“…For example, the asymmetric [3+3] cycloaddition reaction of 2‐(1‐alkynl)‐alk‐2‐en‐1‐one oxime ether 4 with nitrone 2a could furnish the desired product 5 in 83% yield with 89% ee (Eq. 1) . The another asymmetric [4+3] cycloaddition of 1‐(1‐alkynyl)cyclopropyl ketone 6 with nitrone 2a proceeded smoothly to deliver the cycloadduct 7 in 94% yield with 89% ee (Eq.…”

Section: Resultsmentioning

confidence: 99%

Ming‐Phos/Gold(I)‐Catalyzed Stereodivergent Synthesis of Highly Substituted Furo[3,4‐d][1,2]oxazines^†

Zhou

et al. 2020

Chin. J. Chem.

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of main observation and conclusion A gold(I)-catalyzed asymmetric intermolecular tandem [3+3]-cyclization reaction of 2-(1-alkynyl)-2alken-1-ones with nitrones has been developed by using Ming-Phos as a chiral ligand. This method enables access to the stereodivergent synthesis of highly substituted furo[3,4-d][1,2]oxazines in excellent efficiency and stereoselectivity (up to 99% yield, 99% ee, >20 : 1 dr). Scheme 1 Previous results and this work on asymmetric [3+3] cycloaddition of 2-(1-alkynyl)-2-alken-1-ones with nitrones 578 www.cjc.wiley-vch.de

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“…In 2018, we developed the analogous cascade heterocyclization/ [3 + 3]-cycloaddition of 2-(1-alkynyl)alk-2-en-1-one oximes 1−2 and nitrones for the synthesis of heterobicyclic pyrrolo- [3,4-d][1,2]oxazines 38 with excellent stereoselectivity (Scheme 25). 43 This method could be expanded to the gram scale, maintaining the yield and enantioselectivity under the optimal reaction conditions. The reaction was also fascinating due to its extensive substrate scope and good functionality tolerance.…”

Section: Diyne−enonesmentioning

confidence: 99%

Yne–Enones Enable Diversity-Oriented Catalytic Cascade Reactions: A Rapid Assembly of Complexity

Qian

Zhang

2020

Acc. Chem. Res.

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Metrics & More Article RecommendationsCONSPECTUS: A small-molecule collection with structural diversity and complexity is a prerequisite to using either drug candidates or chemical probes for drug discovery and chemical−biology investigations, respectively. Over the past 12 years, we have engaged in developing efficient diversity-oriented cascade strategies for the synthesis of topologically diverse skeletons incorporating biologically relevant structural motifs such as O-and Nheterocycles, fused polycycles, and multifunctionalized allenes. In particular, we have highlighted the use of simple, linear, and densely functionalized molecular platforms in these reactions. This account details our efforts in the design of novel molecular platforms for use in metaland organo-catalyzed cascade reactions, which include 2-(1-alknyl)-2-alken-1-ones (yne− enones) for heterocyclization/cross-coupling cascades, heterocyclization/cycloaddition cascades, nucleophilic addition/cross-coupling cascades, nucleophilic addition/heterocyclization cascades, and so on. Moreover, this Account outlines corresponding mechanistic insights, computational information, and applications of these cascades in the construction of various highly substituted carbo-and heterocycles as well as highly functionalized acyclic compounds, e.g., allenes and dienes. In addition to yne−enones, we evolved the functional groups of our original yne−enones to provide a series of yne−enone variants, which resulted in products with complementary reactivities.The reactivity profile of the yne−enones is defined by the presence of an alkyne moiety and a conjugated enone unit and their mutual through-bond connectivity. Owing to the conceptually rapid development of carbophilic activation, we have identified a series of efficient catalytic systems consisting of metal catalysts, including Pd, Au, and Rh complexes, for diversity-oriented cascade catalysis, allowing various unprecedented reactions to be achieved through different-types of reaction intermediates, including allcarbon metal 1,n-dipoles, furan-based o-quinodimethanes (oQDMs), and allenyl-metal species. In addition to commonly known transition-metal catalytic activity, the Lewis acidity of these complexes is crucial to accomplish the corresponding transformation. In addition, highly enantioselective gold(I)-catalyzed heterocyclization/cycloaddition cascades of yne−enones and their variants were achieved by the application of bisphosphines (e.g., Cn-TunePhos), monophosphines, and our developed "Ming−Phos" as chiral ligands. Importantly, Ming−Phos ligands exhibited excellent performance in gold-catalyzed mechanistically distinct [3 + n]cycloaddition reactions, in which the chiral sulfinamide moiety is possibly responsible for the interaction with the substrate to control enantioselectivity. Subsequently, we demonstrated that the easily prepared polymer-supported Ming−Phos ligand could be applied for heterogeneously gold(I)-catalyzed asymmetric cycloaddition with good stereocontrol. With metal-free catalysis, the d...

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Gold(I)‐Catalyzed Diastereo‐ and Enantioselective Synthesis of Polysubstituted Pyrrolo[3,4‐d][1,2]oxazines

Cited by 14 publications

References 66 publications

Gold-Catalyzed Radical-Involved Intramolecular Cyclization of Internal N-Propargylamides for the Construction of 5-Oxazole Ketones

Gold-Catalyzed Radical-Involved Intramolecular Cyclization of Internal N-Propargylamides for the Construction of 5-Oxazole Ketones

Ming‐Phos/Gold(I)‐Catalyzed Stereodivergent Synthesis of Highly Substituted Furo[3,4‐d][1,2]oxazines^†

Yne–Enones Enable Diversity-Oriented Catalytic Cascade Reactions: A Rapid Assembly of Complexity

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Gold(I)‐Catalyzed Diastereo‐ and Enantioselective Synthesis of Polysubstituted Pyrrolo[3,4‐d][1,2]oxazines

Cited by 14 publications

References 66 publications

Gold-Catalyzed Radical-Involved Intramolecular Cyclization of Internal N-Propargylamides for the Construction of 5-Oxazole Ketones

Gold-Catalyzed Radical-Involved Intramolecular Cyclization of Internal N-Propargylamides for the Construction of 5-Oxazole Ketones

Ming‐Phos/Gold(I)‐Catalyzed Stereodivergent Synthesis of Highly Substituted Furo[3,4‐d][1,2]oxazines†

Yne–Enones Enable Diversity-Oriented Catalytic Cascade Reactions: A Rapid Assembly of Complexity

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Ming‐Phos/Gold(I)‐Catalyzed Stereodivergent Synthesis of Highly Substituted Furo[3,4‐d][1,2]oxazines^†