Chiral Diarylmethanes via Copper-Catalyzed Asymmetric Allylic Arylation with Organolithium Compounds

Guduguntla, Sureshbabu; Hornillos, Valentı́n; Tessier, Romain; Fañanás‐Mastral, Martín; Feringa, Ben L.

doi:10.1021/acs.orglett.5b03396

Cited by 46 publications

(17 citation statements)

References 53 publications

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“… Ma and co-workers have established the enantioselective variant of the process employing 2-methylacetoacetates and simple amino acid ligands such as hydroxyproline . Herein, we report a new class of peptide-based ligands that has culminated in efficient symmetry-breaking cross-coupling reactions for the preparation of enantioenriched, drug-like diarylmethane derivatives 4 . As a system related to eq , these processes fall into the category of reactions with distal pro-stereogenic elements, and our experiments show that the peptide-based catalysts are well-suited for these metal-catalyzed processes.…”

Section: Introductionmentioning

confidence: 87%

Distal Stereocontrol Using Guanidinylated Peptides as Multifunctional Ligands: Desymmetrization of Diarylmethanes via Ullman Cross-Coupling

et al. 2016

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We report the development of a new class of guanidine-containing peptides as multifunctional ligands for transition-metal catalysis and its application in the remote desymmetrization of diarylmethanes via copper-catalyzed Ullman cross-coupling. Through design of these peptides, high levels of enantioinduction and good isolated yields were achieved in the long-range asymmetric cross-coupling (up to 93:7 er and 76% yield) between aryl bromides and malonates. Our mechanistic studies suggest that distal stereocontrol is achieved through a Cs-bridged interaction between the Lewis-basic C-terminal carboxylate of the peptides with the distal arene of the substrate.

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Section: Introductionmentioning

confidence: 87%

Distal Stereocontrol Using Guanidinylated Peptides as Multifunctional Ligands: Desymmetrization of Diarylmethanes via Ullman Cross-Coupling

et al. 2016

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“…Synthesis of (Me 3 Si) 2 HC‐(4‐ t BuOC 6 H 4 )SiCl 2 (2c): A solution of 4‐ t BuOC 6 H 4 Br (2.64 g, 11.5 mmol) in Et 2 O (25 mL) was treated at –78 °C with n BuLi (7.2 mL, 11.5 mmol, 1.6 M in n ‐hexane) to give the respective arylLi which was dropwise added at –78 °C to a solution of (Me 3 Si) 2 HC‐SiCl 3 (3.38 g, 11.5 mmol) in Et 2 O (25 mL). The mixture was warmed to room temperature and stirred overnight.…”

Section: Methodsmentioning

confidence: 99%

Silicon–Halogen Bond Activation in Mixed Si/Al Compounds and an Approach to Intramolecular Stabilized Silylium Ions

et al. 2019

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Alkenylchlorosilanes functionalized by coordinatively unsaturated Al atoms, R′′(R′)Si(Cl)C(AltBu 2 )=C(H)R 5 [R = tBu, cHex, 1-Ad, Ph, 3,5-(F 3 C) 2 C 6 H 3 ; R′ = Mes, Ph, 4-tBuC 6 H 4 , 4-tBuOC 6 H 4 , 4-Et 2 NC 6 H 4 , tBu; R′′ = Mes, CH(SiMe 3 ) 2 , tBu], were obtained in good yields by hydroalumination of the respective alkynylchlorosilanes R′′(R′)Si(Cl)C≡C-R 3 with t Bu 2 Al-H. They feature four-membered, close to planar SiCAlCl heterocycles by intramolecular Al-Cl interactions. The activation of the Si-Cl bonds results in bond lengthening from about 209 pm in 3 to 220 to 225 pm in compounds 5. The 29 Si NMR resonances show an increasing shift to a lower field and range from δ = 24.0 for 5a [R = tBu, R′ = R′′ = Mes] to δ = 68.1 for 5j [R = R′ = R′′ = [a]

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“…In as imilar report by Feringaa nd co-workers,a ryl lithium wasu sed as the aryl nucleophile (Scheme 23). [50] Remarkably, the protocol wasf ound to be highly chemoselective with the halidesa tt he allylic position being arylated in preference to the halogen atom in the aromatic ring. However, n-butyl lithium was found to be essential for the transmetallation reaction.…”

Section: Metal Catalyzed Asymmetric Allylic Alkylationmentioning

confidence: 99%

Overview on the Recent Strategies for the Enantioselective Synthesis of 1, 1‐Diarylalkanes, Triarylmethanes and Related Molecules Containing the Diarylmethine Stereocenter

2018

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There has recently been an increased interest in active pharmaceutical agents and various other molecules that contain the 1, 1‐diaryl stereocenter. This has led to the development of novel synthetic strategies to access molecules having this structural moiety. The current Review describes the variety of synthetic methodologies available for the enantioselective synthesis of 1, 1‐diarylethanes, triarylmethanes and related molecules with a 1, 1‐diaryl stereogenic center that were reported since 1995. The prime focus of the Review is on the formation of the 1, 1‐diarylmethine stereocenter either through the use of various enantioselective processes using chiral catalysts (the asymmetric catalytic approach) or through the use of chiral substrates and achiral catalysts. Resolution of racemic substrates is also required for the synthesis of this chiral molecule, but this approach is not covered in this Review. Moreover, comparative discussions on the future aspects of the synthesis of these molecules with a short comparison of the different available routes and possible areas of development are also presented.

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Chiral Diarylmethanes via Copper-Catalyzed Asymmetric Allylic Arylation with Organolithium Compounds

Cited by 46 publications

References 53 publications

Distal Stereocontrol Using Guanidinylated Peptides as Multifunctional Ligands: Desymmetrization of Diarylmethanes via Ullman Cross-Coupling

Distal Stereocontrol Using Guanidinylated Peptides as Multifunctional Ligands: Desymmetrization of Diarylmethanes via Ullman Cross-Coupling

Silicon–Halogen Bond Activation in Mixed Si/Al Compounds and an Approach to Intramolecular Stabilized Silylium Ions

Overview on the Recent Strategies for the Enantioselective Synthesis of 1, 1‐Diarylalkanes, Triarylmethanes and Related Molecules Containing the Diarylmethine Stereocenter

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