Modular Dihydrobenzoazaphosphole Ligands for Suzuki–Miyaura Cross-Coupling

Zhang, Yongda; Lao, Kendricks S.; Sieber, Joshua D.; Xu, Yibo; Wu, Linglin; Wang, Xiaojun; Desrosiers, Jean‐Nicolas; Lee, Heewon; Haddad, Nizar; Han, Zhengxu S.; Yee, Nathan K.; Song, Jinhua J.; Howell, Amy R.; Senanayake, Chris H.

doi:10.1055/s-0037-1610158

Cited by 6 publications

(9 citation statements)

References 4 publications

(12 reference statements)

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“…Of these methods, the Pd-catalyzed Suzuki–Miyaura and Negishi cross-coupling reactions have received considerable development over the past 40 years. , Significant advances in the development of highly active Pd catalysts to achieve efficient processes have even allowed for these reactions to be employed on an industrial scale . In general, bulky electron-rich phosphines and N-heterocyclic carbenes , have been the ligands of choice to enable these cross-coupling reactions. Despite these advances, cross-coupling catalysts for the formation of sterically demanding biaryls, such as tetra- ortho -substituted systems, remains limited .…”

Section: Introductionmentioning

confidence: 99%

Computationally Assisted Mechanistic Investigation and Development of Pd-Catalyzed Asymmetric Suzuki–Miyaura and Negishi Cross-Coupling Reactions for Tetra-ortho-Substituted Biaryl Synthesis

et al. 2018

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Metal-catalyzed cross-coupling reactions are extensively employed in both academia and industry for the synthesis of biaryl derivatives for applications to both medicine and material science. Application of these methods to prepare tetra-ortho-substituted biaryls leads to chiral atropisomeric products that introduces the opportunity to use catalyst-control to develop asymmetric cross-coupling procedures to access these important compounds. Asymmetric Pd-catalyzed Suzuki-Miyaura and Negishi cross-coupling reactions to form tetra-ortho-substituted biaryls were studied employing a collection of P-chiral dihydrobenzooxaphosphole (BOP) and dihydrobenzoazaphosphole (BAP) ligands. Enantioselectivities of up to 95:5 and 85:15 er were identified for the Suzuki-Miyaura and Negishi cross-coupling reactions, respectively. Unique ligands for the Suzuki-Miyaura reaction vs the Negishi reaction were identified. A computational study on these Suzuki-Miyaura and Negishi cross-coupling reactions enabled an understanding in the differences between the enantiodiscriminating events between these two cross-coupling reactions. These results support that enantioselectivity in the Negishi reaction results from the reductive elimination step, whereas all steps in the Suzuki-Miyaura catalytic cycle contribute to the overall enantioselection with transmetalation and reductive elimination providing the most contribution to the observed selectivities.

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Section: Introductionmentioning

confidence: 99%

Computationally Assisted Mechanistic Investigation and Development of Pd-Catalyzed Asymmetric Suzuki–Miyaura and Negishi Cross-Coupling Reactions for Tetra-ortho-Substituted Biaryl Synthesis

et al. 2018

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“…Our laboratories have been developing novel dihydrobenzooxaphosphole ligands, which have found many applications in valuable organic transformations . On the basis of that, we further developed modular dihydrobenzoazaphosphole ligands possessing high tunability of steric and electronic properties, allowing us to achieve the desired reactivities and stereoselectivities . Recently, piv ZPhos has been emerging as an effective chiral ligand in asymmetric catalysis (Figure ).…”

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confidence: 99%

A Practical Method for the Large-Scale Preparation of the P-Chiral Dihydrobenzoazaphosphole Core by Chemical Resolution

Desrosiers

Kosnik

et al. 2022

J. Org. Chem.

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piv ZPhos, as an effective ligand in the Cu-catalyzed asymmetric hydrogenation of ketones and aminoboration of alkenes, is prepared efficiently from the corresponding triflate of P-chiral dihydrobenzoazaphosphole 1. However, the previous approach to 1 by chiral separation is time-consuming and costly, preventing its production and further application on a large scale. In this report, a practical method for the large-scale preparation of 1 was developed via chiral chemical resolution with (1S,2S)-diaminocyclohexane as an effective resolution reagent.

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“…As part of our ongoing research program, we have reported the synthesis of new modular dihydrobenzoazaphosphole ligands by replacing the oxygen in 2,3-dihydrobenzo[d][1,3]oxaphosphole motif with a nitrogen. 13 This modification improves the tunability of electronic and steric properties of ligands by adjustment of the nitrogen substituting groups. Indeed, the piv ZPhos shows superior reactivity and enantioselectivity to its O-counterpart in the copper-catalyzed asymmetric hydrogenation of 2-substituted ketones 14 and aminoboration of alkenes.…”

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confidence: 99%