Rhodium(<scp>I</scp>)‐Catalyzed Asymmetric Addition of Organometallic Reagents to Unsaturated Compounds

Wu, Hsyueh Liang; Wu, Ping

doi:10.1002/9783527811908.ch5

Cited by 6 publications

(2 citation statements)

References 165 publications

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“…Rhodium-catalyzed asymmetric addition of organoboron reagents to unsaturated compounds is a versatile synthetic method for the construction of optically active compounds via direct C–C bond formation. − This methodology is particularly useful for the preparation of the pivotal intermediates in the synthesis of natural products, therapeutic agents, and so on. To achieve the high levels of enantioselectivity and catalytic activity of these transformations, numerous chiral phosphorus and diene ligands including newly designed and synthesized ones have been employed, and indeed many practically useful protocols have been reported thus far.…”

Section: Applications Of P-stereogenic Phosphorus Ligands In Asymmetr...mentioning

confidence: 95%

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Imamoto

2024

Chem. Rev.

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Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality ligands and P-stereogenic phosphorus ligands. Most of the reported ligands belong to the former class. Privileged ones such as BINAP and DuPhos are frequently employed in a wide range of catalytic asymmetric transformations. In contrast, the latter class of P-stereogenic phosphorus ligands has remained a small family for many years mainly because of their synthetic difficulty. The late 1990s saw the emergence of novel P-stereogenic phosphorus ligands with their superior enantioinduction ability in Rh-catalyzed asymmetric hydrogenation reactions. Since then, numerous P-stereogenic phosphorus ligands have been synthesized and used in catalytic asymmetric reactions. This Review summarizes P-stereogenic phosphorus ligands reported thus far, including their stereochemical and electronic properties that afford high to excellent enantioselectivities. Examples of reactions that use this class of ligands are described together with their applications in the construction of key intermediates for the synthesis of optically active natural products and therapeutic agents. The literature covered dates back to 1968 up until December 2023, centering on studies published in the late 1990s and later years.

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Section: Applications Of P-stereogenic Phosphorus Ligands In Asymmetr...mentioning

confidence: 95%

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Imamoto

2024

Chem. Rev.

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“…The use of a lithium, zinc, or titanium reagent instead of a magnesium reagent did not give a high yield of the product 2a (entries 10–12). The corresponding pinacolborane reagent is not reactive under the present reaction conditions (THF, 25 °C; entry 13), and it underwent protodeborylation under one of the standard conditions (in dioxane/H 2 O/KOH at 80 °C) for rhodium-catalyzed asymmetric conjugate addition of organoboron reagents (entry 14).…”

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confidence: 99%

Desymmetrization of 2-(1,5-Dialkoxypent-3-yl)phenyl Grignard Reagents by Rhodium-Catalyzed Asymmetric 1,4-Shift/β-Alkoxy Elimination

Tsai,

Chen,

Sun

et al. 2024

ACS Catal.

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Cyclobutadiene Rhodium Complexes as Catalysts for the Synthesis of Amides from Electron‐rich Arenes, Tosyl Azide and CO

2021

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Cyclobutadiene rhodium complexes [(C4R4)RhX]2 (R=Et, Ph; X=I, Cl) at 0.5 mol % loading catalyze the formation of aromatic amides from various indoles, tosyl azide, and carbon monoxide (1 atm). The reaction gives good yields of the target products (typically 60–85 %) and tolerates both donor and moderately acceptor substituents in the indoles (alkyl, OMe, Hal, COOMe, but not CN). The DFT calculations at the PBE/3ζ level revealed a new plausible mechanism for the reaction of TsN3 with CO via cycloaddition and formation of RhCON3 metallacycle, which is more favorable than the commonly assumed formation of nitrene intermediate.

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Rhodium(I)‐Catalyzed Asymmetric Addition of Organometallic Reagents to Unsaturated Compounds

Cited by 6 publications

References 165 publications

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Desymmetrization of 2-(1,5-Dialkoxypent-3-yl)phenyl Grignard Reagents by Rhodium-Catalyzed Asymmetric 1,4-Shift/β-Alkoxy Elimination

Cyclobutadiene Rhodium Complexes as Catalysts for the Synthesis of Amides from Electron‐rich Arenes, Tosyl Azide and CO

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