Utilization of BozPhos as an Effective Ligand in Enantioselective C–H Functionalization of Cyclopropanes: Synthesis of Dihydroisoquinolones and Dihydroquinolones

Mayer, Camilla; Ladd, Carolyn L.; Charette, André B.

doi:10.1021/acs.orglett.9b00627

Cited by 18 publications

(14 citation statements)

References 72 publications

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“…Three years later, the same group reported the application of BozPhos to the enantioselective synthesis of cyclopropane‐fused dihydroisoquinolones and dihydroquinolones (Scheme 32). [89] They used benzamide 70 a as a model substrate for the reaction optimization. Several Pd sources were evaluated and Buchwald's fourth‐generation palladium dimer (Pd‐G4) [90] resulted in an excellent yield and enantioselectivity.…”

Section: Bidentate and Hemilabile 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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Section: Bidentate and Hemilabile 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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“…A switch to acetonitrile as solvent further improved the er to 85.5:14.5 with a significantly increased yield of 65% (entry 7). Different bisphosphine monoxides (BPMOs) such as SEGPHOSO ( L7 ), SYNPHOSO ( L8 ), DIFLUORPHOSO ( L9 ), MeOBIPHEPO ( L10 ), and H 8 -BINAPO ( L11 ) were prepared through a modified Grushin protocol in a single step . Notably, the BPMO ligand type preferentially provided the opposite enantiomer compared to the MOP ligands.…”

mentioning

confidence: 99%

Intermolecular Palladium(0)-Catalyzed Atropo-enantioselective C–H Arylation of Heteroarenes

et al. 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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“…Inspired by this work, Charette and coworkers explored BINOL-derived phosphoramidite (R)-IPrMonophos and BozPhos bidentate ligands in related alkenylation reactions instead of arylation processes, obtaining moderate to good ees (Scheme 23d) [57]. In 2019, they published an article demonstrating the efficiency of BozPhos ligands in Cramer's reaction (synthesis of dihydroquinolones and dihydroisoquinolones, Scheme 23e) [58].…”

Section: Activation Of C(sp 3 )--H Bondsmentioning

confidence: 99%

Transition Metal‐Catalyzed Desymmetrizations Based on CH Activation Processes

Vidal

Font

Gulı́as

et al. 2022

Handbook of CH-Functionalization

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The relevance of chiral pharmaceuticals and fine chemicals has encouraged the development of synthetic methods that allow the preparation of these products in enantioselective form. Of the different strategies, those relying on the metal‐catalyzed enantioselective activation of CH bonds are especially appealing, owing to their step and atom economy. This is particularly the case in desymmetrization approaches, because of the simplicity of the reactants, and their intrinsic complexity increase characteristics. This article reviews the current state of the art on transition metal‐catalyzed desymmetrizing functionalizations involving enantiodetermining CH activation steps.

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Utilization of BozPhos as an Effective Ligand in Enantioselective C–H Functionalization of Cyclopropanes: Synthesis of Dihydroisoquinolones and Dihydroquinolones

Cited by 18 publications

References 72 publications

Chiral Catalysts for Pd⁰‐Catalyzed Enantioselective C−H Activation

Chiral Catalysts for Pd⁰‐Catalyzed Enantioselective C−H Activation

Intermolecular Palladium(0)-Catalyzed Atropo-enantioselective C–H Arylation of Heteroarenes

Transition Metal‐Catalyzed Desymmetrizations Based on CH Activation Processes

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Utilization of BozPhos as an Effective Ligand in Enantioselective C–H Functionalization of Cyclopropanes: Synthesis of Dihydroisoquinolones and Dihydroquinolones

Cited by 18 publications

References 72 publications

Chiral Catalysts for Pd0‐Catalyzed Enantioselective C−H Activation

Chiral Catalysts for Pd0‐Catalyzed Enantioselective C−H Activation

Intermolecular Palladium(0)-Catalyzed Atropo-enantioselective C–H Arylation of Heteroarenes

Transition Metal‐Catalyzed Desymmetrizations Based on CH Activation Processes

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Chiral Catalysts for Pd⁰‐Catalyzed Enantioselective C−H Activation

Chiral Catalysts for Pd⁰‐Catalyzed Enantioselective C−H Activation