Palladium catalyzed asymmetric Suzuki–Miyaura coupling reactions to axially chiral biaryl compounds: Chiral ligands and recent advances

Zhang, Dao; Wang, Quanrui

doi:10.1016/j.ccr.2014.11.011

Cited by 249 publications

(39 citation statements)

References 70 publications

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“…We then investigated the performance of L1 and L2 in the asymmetric SMC reaction45464748495051 between diisopropyl (1-bromonaphthalen-2-yl) phosphonate 15a and o -tolylboronic acid 16 a under optimized reaction conditions (Pd(OAc) 2 / L* /toluene/50 °C, see Table S3, Supplementary Information). As shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

Rational Design and Synthesis of [5]Helicene-Derived Phosphine Ligands and Their Application in Pd-Catalyzed Asymmetric Reactions

Yamamoto

Shimizu

Igawa

et al. 2016

Sci Rep

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A series of novel optically active [5]helicene-derived phosphine ligands (L1, with a 7,8-dihydro[5]helicene core structure- and L2, with a fully aromatic [5]helicene core structure) were synthesized. Despite their structural similarities, L1 and L2 exhibit particularly different characteristics in their use as chiral ligands. L1 was highly effective in the asymmetric allylation of indoles with 1,3-diphenylallyl acetate (up to 99% ee), and in the etherification of alcohols (up to 96% ee). In contrast, L2 was highly effective in the stereocontrol of helical chirality in Suzuki–Miyaura coupling (SMC) reaction (up to 99% ee). Density functional theory analysis was employed to propose a model that accounts for the origin of the enantioselectivity in these reactions.

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Section: Resultsmentioning

confidence: 99%

Rational Design and Synthesis of [5]Helicene-Derived Phosphine Ligands and Their Application in Pd-Catalyzed Asymmetric Reactions

Yamamoto

Shimizu

Igawa

et al. 2016

Sci Rep

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“…Thus, the axis of a stable biaryl atropisomer is usually sterically congested, and its construction is challenging. Because of their importance and widespread applications in both medicinal and synthetic chemistry, a number of strategies for the construction of biaryl atropisomers have been developed, including metal-catalyzed asymmetric cross-coupling, [7][8][9][10][11] asymmetric ''aromatic substitution,'' 12 and de novo aromatic ring formation (such as asymmetric [2 + 2 + 2] cycloaddition). [13][14][15] In addition, modification of the existing biaryl structures enables access to enantio-enriched atropisomers via either a desymmetrization reaction or (dynamic) kinetic resolution (Scheme 1D).…”

Section: Introductionmentioning

confidence: 99%

Enhanced Reactivity by Torsional Strain of Cyclic Diaryliodonium in Cu-Catalyzed Enantioselective Ring-Opening Reaction

Zhao

Duan

et al. 2018

Chem

194

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An efficient method is developed for preparing functionalized axially chiral compounds via the ring-opening reaction of cyclic diaryliodonium salts. Two conformers of the cyclic diaryliodonium salt observed in the crystal structure underwent quick equilibration. The distortion of the diaryliodonium salts significantly increased reactivity toward the chiral copper catalyst, which enabled the reaction to take place in mild conditions to furnish the products in enantioselectivities up to 99.5:0.5 (R:S).

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“…Herein, we would like to demonstrate that SDE is a common phenomenon observed during the achiral low-pressure column chromatography of the chiral compounds obtained in benchmark asymmetric reactions such as allylic substitution, [46,47] cross-coupling [48][49][50][51][52] and organocatalytic aldol condensation [53,54] as well as other important asymmetric transformations. Thus, such processes may play a significant role in the course of the chiral, non-racemic, pro-biotic compound formation.…”

Section: Introductionmentioning

confidence: 99%

A General Phenomenon of Spontaneous Amplification of Optical Purity under Achiral Chromatographic Conditions

et al. 2019

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This work explores the behavior of chiral compound mixtures enriched in one of the enantiomers whilst a typical chromatography on the achiral stationary phase is employed. The influence of several factors, such as the eluent composition, ratio of the compound to the stationary phase, and the initial enatiomeric purity of the compound used on the distribution of the enantiomers in the collected chromatographic fraction, was studied. The obtained results indicate that the phenomenon of Self Disproportionation of Enantiomer (SDE) occurred in all cases, and some of the collected fractions got higher optical purities than the initial one. Thus, achiral column chromatography could be applied in some cases as the simplest approach for chiral purification. Based on the experimental results and DFT calculations, an alternative concept explaining the SDE phenomenon was proposed. Due to its generality and simplicity, SDE may also be responsible for the formation of the first chiral non-racemic compounds on the early Earth.

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Palladium catalyzed asymmetric Suzuki–Miyaura coupling reactions to axially chiral biaryl compounds: Chiral ligands and recent advances

Cited by 249 publications

References 70 publications

Rational Design and Synthesis of [5]Helicene-Derived Phosphine Ligands and Their Application in Pd-Catalyzed Asymmetric Reactions

Rational Design and Synthesis of [5]Helicene-Derived Phosphine Ligands and Their Application in Pd-Catalyzed Asymmetric Reactions

Enhanced Reactivity by Torsional Strain of Cyclic Diaryliodonium in Cu-Catalyzed Enantioselective Ring-Opening Reaction

A General Phenomenon of Spontaneous Amplification of Optical Purity under Achiral Chromatographic Conditions

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