Asymmetric Hydroformylation Using Rhodium

Cunillera, Anton; Godard, Cyril; Ruiz, Aurora

doi:10.1007/3418_2017_176

Cited by 11 publications

(3 citation statements)

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“…Among the many asymmetric carbon–carbon bond-forming reactions promoted by rhodium catalysts, asymmetric hydroformylation (AHF) is an industrially important process for the production of optically active aldehydes and their derivatives from inexpensive feedstocks (alkenes and syngas). − Most of the chiral ligands used for Rh-catalyzed AHF are backbone chirality phosphines, phosphites, or their hybrid bisphosphorus units, and many successful results have been reported. On the other hand, several research groups have disclosed unique and synthetically valuable Rh-catalyzed AHF reactions, using P-stereogenic phosphorus ligands ( L29 , TangPhos, , Binapine, BenzP*, DuanPhos, QuinoxP*, , L80 , BettiPhos, and BIBOP , ).…”

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

confidence: 99%

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: 99%

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Imamoto

2024

Chem. Rev.

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“…1 As a result, developing efficient methods, especially stereoselective ones, for the synthesis of a diverse range of 3-methylene-indolinones is unarguably critical for continued progress in the area of drug development. 3–9 Despite this growing demand, the stereoselective construction of the substituted methylene moiety of 3-methylene-oxindoles has been a longstanding challenge and, for these reasons, highly stereoselective preparation methods remain rare to date. Classical approaches for the assembly of methylene oxindoles mainly involve the intermolecular condensation of oxindoles with aryl carbonyl compounds, including diaryl ketones and aromatic formaldehydes, but these transformations face serious stereoselective control issues and substrate scope limitations.…”

Section: Introductionmentioning

confidence: 99%

“…Classical approaches for the assembly of methylene oxindoles mainly involve the intermolecular condensation of oxindoles with aryl carbonyl compounds, including diaryl ketones and aromatic formaldehydes, but these transformations face serious stereoselective control issues and substrate scope limitations. 1,3 To overcome these issues, transition-metal-catalyzed tandem annulation reactions with unsaturated hydrocarbons, 4 such as cross-coupling-enabled annulation cascades of N -(2-haloaryl)propiolamides, 5 N -arylpropiolamides, 6 or 2-(alkynyl)arylisocyanates; 7 the carbonylative annulation of 2-alkynylanilines or 2-alkenylanilines; 8 the chloroacylation of alkyne-tethered carbamoyl chlorides; 9 and the cross-dehydrogenation coupling (CDC) of 2,3-diarylacrylamides or N -cinnamoylanilines, 10 have been developed. Common transition-metal catalysts (such as those containing Pd, Rh, Co 2 Rh 2 , and Ni) are efficient for use in these transformations to access various functionalized 3-methylene-oxindoles; however, the careful control of stereoselectivity sometimes remains a problem, with most configurations being unknown before the conclusion of the reaction.…”

Section: Introductionmentioning

confidence: 99%