Inverse‐Electron‐Demand Palladium‐Catalyzed Asymmetric [4+2] Cycloadditions Enabled by Chiral P,S‐Ligand and Hydrogen Bonding

Wang, Yani; Xiong, Qin; Lu, Liang‐Qiu; Zhang, Qun-Liang; Wang, Ying; Lan, Yu; Xiao, Wen‐Jing

doi:10.1002/anie.201905993

Cited by 91 publications

(26 citation statements)

References 76 publications

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“…Another notable example of a [4+2] cycloaddition can be found in the synthesis of dihydroquinol-2-ones through reaction of vinyl carbamates with deconjugated butenolides and azlactones as nucleophilic dipolarophiles ( Scheme 304 ). 739 The success of this transformation was attributed to the use of chiral phosphoramidite-thioether ligand L169 and control of the regioselectivity by a hydrogen bonding interaction.…”

Section: Cyclization Reactions Via Pd-catalyzed Interceptive Asymmetric Allylic Substitutionmentioning

confidence: 99%

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

407

202

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This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution and decarboxylative and oxidative allylic substitutions. For each reaction, the catalytic data, as well as examples of their application to the synthesis of more complex molecules, are collected. Sections in which we discuss key mechanistic aspects for high selectivity and a comparison with other metals (with advantages and disadvantages) are also included. For Pd-catalyzed asymmetric allylic substitution, the catalytic data are grouped according to the type of nucleophile employed. Because of the prominent position of the use of stabilized carbon nucleophiles and heteronucleophiles, many chiral ligands have been developed. To better compare the results, they are presented grouped by ligand types. Pd-catalyzed asymmetric decarboxylative reactions are mainly promoted by PHOX or Trost ligands, which justifies organizing this section in chronological order. For asymmetric oxidative allylic substitution the results are grouped according to the type of nucleophile used.

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Section: Cyclization Reactions Via Pd-catalyzed Interceptive Asymmetric Allylic Substitutionmentioning

confidence: 99%

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

407

202

View full text Add to dashboard Cite

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“…With the introduction of cyclic imines or barbiturate-based olefin reactants, it is feasible to construct highly functionalized quinazolines through decarboxylative cycloadditions [11][12][13]. Most recently, the annulation of deconjugated butenolides or azlactones with vinyl carbamates towards highly functionalized chiral dihydroquinol-2-ones was released by the Xiao group [14]. It was found that the utilization of the newly exploited chiral P,S-ligand and hydrogen bonding is the key to control the regioselectivity for this reaction.…”

Section: Introductionmentioning

confidence: 99%

An Update of Transition Metal-Catalyzed Decarboxylative Transformations of Cyclic Carbonates and Carbamates

Zuo

Chang

et al. 2019

Molecules

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Functionalized cyclic organic carbonates and carbamates are frequently used in a number of transition metal-catalyzed decarboxylative reactions for the construction of interesting molecules. These decarboxylative transformations have attracted more and more research attention in recent years mainly due to their advantages of less waste generation and versatile reactivities. On the basis of previous reviews on this hot topic, the present review will focus on the development of transition metal-catalyzed decarboxylative transformations of functionalized cyclic carbonates and carbamates in the last two years.

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“…As illustrated in Figure A, chiral ligand L2 bearing a biphenyl phosphoramidite unit, which had a good performance in our previous asymmetric [4+2] dipolar cycloadditions of vinyl benzoxazinones and ketenes, can also promote this asymmetric higher‐order cycloaddition in a good efficiency and enantioselectivity ( L2 : 95 % yield, 14:86 er). The use of 3,3′‐modified BINOL‐derived P,S ligands L3 and L4 , which gave the best results in our recently reported Pd‐catalyzed asymmetric [4+2] cycloadditions and Cu‐catalyzed asymmetric [3+2] cycloadditions, could not provide better results on the enantioselectivity ( L3 : 86 % yield, 86:14 er; L4 : 74 % yield, 80:20 er). Next, these chiral P,S ligands were modified to further improve the stereoselectivity.…”

Section: Figurementioning

confidence: 85%

Palladium‐Catalyzed Asymmetric [8+2] Dipolar Cycloadditions of Vinyl Carbamates and Photogenerated Ketenes

Zhang

Xiong

et al. 2020

Angewandte Chemie

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Higher-order cycloadditions, particularly [8+2] cycloadditions, are a straightforward and efficient strategy for constructing significant medium-sized architectures. Typically, configuration-restrained conjugated systems are utilized as 8pcomponents for higher-order concerted cycloadditions. However, for this reason, 10-membered monocyclic skeletons have never been constructed via catalytic asymmetric [8+2] cycloaddition with high peri-and stereoselectivity. Here, we accomplished an enantioselective [8+2] dipolar cycloaddition via the merger of visible-light activation and asymmetric palladium catalysis. This protocol provides a new route to 10membered monocyclic architectures bearing chiral quaternary stereocenters with high chemo-, peri-, and enantioselectivity. The success of this strategy relied on the facile in situ generation of Pd-containing 1,8-dipoles and their enantioselective trapping by ketene dipolarophiles, which were formed in situ via a photo-Wolff rearrangement. Over the past six decades, the importance of higher-order cycloadditions for the construction of medium-sized heterocyclic skeletons has been demonstrated. [1] In this context, since the first work from Doering and Wiley in 1960, [2] a variety of [8+2] cycloadditions have been developed. [3] These transformations usually require configurationrestrained, conjugated 8p-components [4-6] to reduce the reaction complexity and entropic barriers, i.e., to disfavour intramolecular cyclizations and facilitate the periselectivity.

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Inverse‐Electron‐Demand Palladium‐Catalyzed Asymmetric [4+2] Cycloadditions Enabled by Chiral P,S‐Ligand and Hydrogen Bonding

Cited by 91 publications

References 76 publications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

An Update of Transition Metal-Catalyzed Decarboxylative Transformations of Cyclic Carbonates and Carbamates

Palladium‐Catalyzed Asymmetric [8+2] Dipolar Cycloadditions of Vinyl Carbamates and Photogenerated Ketenes

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