Chiral Bifunctional Phosphine‐Carboxylate Ligands for Palladium(0)‐Catalyzed Enantioselective C−H Arylation

Yang, Lei; Neuburger, Markus; Baudoin, Olivier

doi:10.1002/anie.201712061

Cited by 65 publications

(29 citation statements)

References 54 publications

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“…(R)-6-((2'-(Diphenylphosphaneyl)-[1,1'-binaphthalen]-2-yl)oxy)hexanoic acid (L5): Synthesized according to reported procedure. 3 Spectral data are in agreement with reported literature.…”

Section: S7supporting

confidence: 91%

Intermolecular Palladium-Catalyzed Atropo-Enantioselective C–H Arylation of Heteroarenes

2020

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General Methods Experimental Procedures, Reagents and Glassware All commercially available chemicals were used as purchased for the synthesis of substrates. All reactions were carried out under an atmosphere of nitrogen in oven-dried glassware with magnetic stirring, unless otherwise indicated. Acetonitrile (MeCN) was dried over CaH2, distilled and stored inside the N2-filled glovebox. Toluene, THF and dichloromethane were purified by the Innovative Technology Solvent Delivery System. Chemicals were used as obtained from the suppliers unless otherwise stated. Solvent compositions are given in (v/v). Chromatography Flash chromatography was performed with Silicycle silica gel 60 (0.040-0.063 μm grade). Analytical thin-layer chromatography was performed with commercial glass plates coated with 0.25 mm silica gel (E. Merck, Kieselgel 60 F254). Compounds were visualized under UV-light at 254 nm and oxidized in standard KMnO4 dye followed by heating if necessary. NMR Spectroscopy Proton nuclear magnetic resonance (1 H NMR) data were acquired at 400 MHz on a Bruker AVANCEIII-400 spectrometer or at 600 MHz on a Bruker DRX-600 spectrometer. Chemical shifts (δ) are reported in parts per million (ppm) relative to residual chloroform (s, 7.26 ppm) or residual acetone (2.05 ppm). Proton decoupled Carbon-13 nuclear magnetic resonance (13 C NMR) data were acquired at 101 MHz or 126 MHz on a Bruker AVANCEIII-400. Chemical shifts are reported in ppm relative to residual chloroform (77.16 ppm) or residual acetone (29.84 ppm, 206.26 ppm). Proton decoupled Fluorine-19 nuclear magnetic resonance (19 F{ 1 H} NMR) were acquired at 377 MHz on a Bruker AV400 spectrometer. Proton decoupled Phosphorus-31 nuclear magnetic resonance (31P{1H} NMR) were acquired at 162 MHz on a Bruker AV400 spectrometer. The assignment of proton and carbon signals was assisted by COSY, HSQC, HMBC and DEPT-135 experiments where necessary. Splitting patterns are designated as s, singlet; d, doublet; t, triplet; q, quartet; p, pentet; hept, heptet; dd, doublet of doublets; dt, doublet of triplets; ddd, doublet of doublets of doublets; tt, triplet of triplets; tq, triplet of quartets; qt, quartet of triplets; m, multiplet. All NMR data were recorded at 298 K. Infrared Spectroscopy Infrared (IR) data were recorded on an Alpha-P Bruker FT-IR Spectrometer. Absorbance frequencies are reported in reciprocal centimeters (cm-1). Mass Spectrometry HRMS measurements were performed on an Agilent LC-MS TOF (Multimode: ESI + APCI + APPI). High resolution mass are given in m/z. Melting Points Melting points were measured on a Büchi B-540 and are uncorrected. Enantiomeric excesses Enantiomeric excesses were measured on an Agilent HPLC and Shimadzu HPLC. Optical rotations were measured on a Polartronic M polarimeter using a 0.5 cm cell with a Na 589 nm filter.

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“…(R)-6-((2'-(Diphenylphosphaneyl)-[1,1'-binaphthalen]-2-yl)oxy)hexanoic acid (L5): Synthesized according to reported procedure. 3 Spectral data are in agreement with reported literature.…”

Section: S7supporting

confidence: 91%

Intermolecular Palladium-Catalyzed Atropo-Enantioselective C–H Arylation of Heteroarenes

2020

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“…In contrast to Pd II catalysis, the use of bifunctional ligands in Pd 0 ‐catalyzed C−H activation has remained unknown for a long time. In 2018, our group reported the first example of Pd 0 ‐catalyzed intramolecular C−H arylation using a bifunctional ligand [119] . The design of the latter was based on MOP‐type ligands, [120] with a chiral binaphthyl scaffold substituted on one side with a phosphine and on the other with a carboxylic acid (Scheme 49).…”

Section: Chiral Bases and Bifunctional Ligandsmentioning

confidence: 99%

“…In 2018, our group reported the first example of Pd 0 -catalyzed intramolecularC ÀHa rylation using ab ifunctional ligand. [119] The design of the latter was based on MOP-type ligands, [120] with ac hiral binaphthyl scaffold substituted on one side with ap hosphine and on the other with ac arboxylic acid (Scheme 49). Monofunctional ligandss uch as MOP,a ne stersubstituted MOP (L 33 ), but also other classic chiral ligandss uch as TADDOL-based phosphoramidite L 2 ,B INAP,a nd NHCs, provided lower enantioselectivities in combination with an external carboxylic acid.Further investigations revealed that the distance between the carboxylic group and the binaphthalene scaffold was important fort he enantioselectivity (L 34 -L 36 ), with an optimum for MOP-acetic acidh ybrid ligand L 34 .A dditional adjustments of the phosphorus aryl substituents allowed not only the yield to be improved, but also the enantioselectivity to be increased (L 37 ,e .r.9 7.5:2.5).…”

Section: Bifunctional Ligandsmentioning

confidence: 99%

Chiral Catalysts for Pd⁰‐Catalyzed Enantioselective C−H Activation

Vyhivskyi

Kudashev

Miyakoshi

et al. 2020

Chemistry A European J

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In the past few decades, processes that involve transition-metal catalysis have represented am ajor parto f the synthetic chemist'st oolbox. Recently,t he interesth as shifted from the well-established cross-coupling reactions to CÀHb ond functionalization, thus making it ac urrent frontier of transition-metal-catalyzed reactions. Constant progress in this field has led to the discoveryo fe nantioselective methods to generate and control various types of stereogenic elements, thereby demonstrating its high value to generate scalemic chiral molecules.The present review is dedicated to enantioselective Pd 0-catalyzed CÀHa ctivation,w hich may be considered as an evolution of Pd 0-catalyzed cross-couplings, with af ocus on the different chiral ligands and catalysts that enable theset ransformations.

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“…To induce a more organized transition state, and thereby to provide higher enantioselectivities in challenging cases, we recently developed a new family of chiral bifunctional phosphine‐carboxylate ligands (Scheme 1 a). [8] Herein, we describe the application of this approach to the enantioselective synthesis of highly symmetrical fluoradenes, [9] through the selective activation of one enantiotopic C−H bond (Scheme 1 b), and other warped molecules, which could serve to the bottom‐up preparation of buckybowls or other bowl‐shaped hydrocarbons.…”

Section: Methodsmentioning

confidence: 99%

Enantioselective Pd⁰‐Catalyzed C(sp²)–H Arylation for the Synthesis of Chiral Warped Molecules

Savary

Baudoin

2021

Angewandte Chemie

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C−H activation‐based ring‐forming methods are a powerful approach for the construction of complex molecular architectures, especially those containing a congested stereocenter. Therefore, this strategy seems perfectly suited to address the synthesis of chiral polycyclic aromatic hydrocarbons (PAHs) and bowl‐shaped molecules, which are important target molecules in the field of organic electronic materials. Herein, we describe an enantioselective Pd0‐catalyzed C(sp2)−H arylation protocol for the synthesis of chiral fluoradenes and other warped molecules, which could serve to the bottom‐up construction of chiral PAHs. The current approach relies on the use of chiral bifunctional phosphine–carboxylate ligands and delivers diverse polycyclic compounds in high yield and with good to excellent enantioselectivity. The chiroptical properties of the obtained products were investigated, and some of them were found to have a strong ellipticity and an emission band located in the visible region.

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Chiral Bifunctional Phosphine‐Carboxylate Ligands for Palladium(0)‐Catalyzed Enantioselective C−H Arylation

Cited by 65 publications

References 54 publications

Intermolecular Palladium-Catalyzed Atropo-Enantioselective C–H Arylation of Heteroarenes

Intermolecular Palladium-Catalyzed Atropo-Enantioselective C–H Arylation of Heteroarenes

Chiral Catalysts for Pd⁰‐Catalyzed Enantioselective C−H Activation

Enantioselective Pd⁰‐Catalyzed C(sp²)–H Arylation for the Synthesis of Chiral Warped Molecules

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Chiral Bifunctional Phosphine‐Carboxylate Ligands for Palladium(0)‐Catalyzed Enantioselective C−H Arylation

Cited by 65 publications

References 54 publications

Intermolecular Palladium-Catalyzed Atropo-Enantioselective C–H Arylation of Heteroarenes

Intermolecular Palladium-Catalyzed Atropo-Enantioselective C–H Arylation of Heteroarenes

Chiral Catalysts for Pd0‐Catalyzed Enantioselective C−H Activation

Enantioselective Pd0‐Catalyzed C(sp2)–H Arylation for the Synthesis of Chiral Warped Molecules

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Chiral Catalysts for Pd⁰‐Catalyzed Enantioselective C−H Activation

Enantioselective Pd⁰‐Catalyzed C(sp²)–H Arylation for the Synthesis of Chiral Warped Molecules