Enantioselective Nickel-Catalyzed Hydrocyanative Desymmetrization of Norbornene Derivatives

Sun, Feilong; Wang, Ting; Cheng, Gui‐Juan; Fang, Xianjie

doi:10.1021/acscatal.1c01971

Cited by 27 publications

(9 citation statements)

References 54 publications

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“…Among the strategies, desymmetrization of configurationally stable and symmetric biaryls can provide an alternative and efficient way to approach axially chiral molecules (Fig. 1b) [32][33][34][35][36][37][38][39][40][41][42][43][44] . However, compared to other strategies, a limited number of reactions have been reported, which represents the current cutting edge of this type of reaction [33][34][35][36][37][38][39][40][41][42][43][44] .…”

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confidence: 99%

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Atroposelective desymmetrization of 2-arylresorcinols via Tsuji-Trost allylation

Kim

Lee

et al. 2023

Commun Chem

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Palladium-catalyzed asymmetric allylic alkylation has proven to be a powerful method for the preparation of a wide variety of chiral molecules. However, the catalytic and atroposelective allylic alkylation is still rare and challenging, especially for biaryl substrates. Herein, we report the palladium-catalyzed desymmetric and atroposelective allylation, in which the palladium complex with a chiral phosphoramidite ligand enables desymmetrization of nucleophilic 2-arylresorcinols in a highly enantioselective manner. With the aid of the secondary kinetic resolution effect, a wide variety of substrates containing a hydroxymethyl group at the bottom aromatic ring are able to provide O-allylated products up to 98:2 er. Computational studies show an accessible quadrant of the allylpalladium complex and provide three plausible transition states with intra- or intermolecular hydrogen bonding. The energetically favorable transition state is in good agreement with the observed enantioselectivity and suggests that the catalytic reaction would proceed with an intramolecular hydrogen bond.

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confidence: 99%

“…1b) [32][33][34][35][36][37][38][39][40][41][42][43][44] . However, compared to other strategies, a limited number of reactions have been reported, which represents the current cutting edge of this type of reaction [33][34][35][36][37][38][39][40][41][42][43][44] .…”

mentioning

confidence: 99%

Atroposelective desymmetrization of 2-arylresorcinols via Tsuji-Trost allylation

Kim

Lee

et al. 2023

Commun Chem

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“…The highly ring-strain-demanding observation promoted us to further study the diastereo- and enantioselectivities of the (3 + 2) transannulations of a series of norbornene derivatives (Scheme d) . Under iridium catalysis, which was demonstrated to be incapable in previous reports, − the (3 + 2) transannulations exclusively take place at the exo side of norbornene derivatives to deliver polycyclic cis -2,3-dihydrothiophenes in a diastereospecific manner.…”

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confidence: 79%

Catalytic Diastereospecific and Enantioselective (3 + 2) Transannulations of 1,2,3-Thiadiazoles with Strained Norbornene Derivatives

et al. 2022

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“…Lastly, axially chiral N ‐aryl succinimides 170 have been prepared from N ‐aryl 5‐norbornene‐2,3‐dicarboximides 168 using a nickel‐catalyzed enantioselective hydrocyanation with cyanohydrin 169 as a hydrogen cyanide surrogate (Scheme 51). [83] The desymmetrization process proceeds with generation of central and remote N−C axial chirality, reaching high levels of enantioselectivity by using ( R )‐DM‐SEGPHOS ligand ent ‐ L11 . The absence of a nonlinear effect (NLE) suggests that a monomeric [Ni L11 ] complex is the catalytically active species, and control experiments confirmed the key role of the carbonyl groups of the substrate.…”

Section: N‐aryl Five‐membered Heterocyclesmentioning

confidence: 99%

Asymmetric Synthesis of Axially Chiral C−N Atropisomers

Rodríguez‐Salamanca

Fernández

Hornillos

et al. 2022

Chemistry A European J

120

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Molecules with restricted rotation around a single bond or atropisomers are found in a wide number of natural products and bioactive molecules as well as in chiral ligands for asymmetric catalysis and smart materials. Although most of these compounds are biaryls and heterobiaryls displaying a CÀ C stereogenic axis, there is a growing interest in less common and more challenging axially chiral CÀ N atropisomers. This review offers an overview of the various methodologies available for their asymmetric synthesis. A brief introduction is initially given to contextualize these axially chiral skeletons, including a historical background and examples of natural products containing axially chiral CÀ N axes. The preparation of different families of CÀ N based atropisomers is then presented from anilides to chiral fiveand six-membered ring heterocycles. Special emphasis has been given to modern catalytic asymmetric strategies over the past decade for the synthesis of these chiral scaffolds. Applications of these methods to the preparation of natural products and biologically active molecules will be highlighted along the text.

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Enantioselective Nickel-Catalyzed Hydrocyanative Desymmetrization of Norbornene Derivatives

Cited by 27 publications

References 54 publications

Atroposelective desymmetrization of 2-arylresorcinols via Tsuji-Trost allylation

Atroposelective desymmetrization of 2-arylresorcinols via Tsuji-Trost allylation

Catalytic Diastereospecific and Enantioselective (3 + 2) Transannulations of 1,2,3-Thiadiazoles with Strained Norbornene Derivatives

Asymmetric Synthesis of Axially Chiral C−N Atropisomers

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