Regio- and Stereoselective Addition of Secondary Phosphine Oxides to Allenoates Catalyzed by Main-Group Lewis Pairs

Kwak, Soojin; Choi, Jeongin; Han, Jimin; Lee, Sarah Yunmi

doi:10.1021/acscatal.1c04242

Cited by 13 publications

(2 citation statements)

References 76 publications

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“…In addition, 2,3-allenamides also serve as versatile building blocks in organic synthesis due to their unique structure and reactivity. With a unique orthogonal cumulative π-system, this structure has been widely used in a range of transformations, such as cyclization reactions, nucleophilic and radical addition reactions, and cycloaddition reactions …”

Section: Introductionmentioning

confidence: 99%

Synthesis of Multisubstituted 2,3-Allenamides via Palladium-Catalyzed Carbonylation of Propargylic Esters

Zhang,

Ji,

et al. 2024

J. Org. Chem.

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2,3-Allenamides are an important class of unsaturated group-substituted carbonyl compounds. A palladiumcatalyzed aminocarbonylation of propargyl acetates with amines for the synthesized tri-/tetrasubstituted 2,3-allenamides has been developed. A broad range of tri-/tetrasubstituted 2,3-allenamides have been prepared from propargyl acetates in good to excellent yields. The reaction featured mild reaction conditions and good functional group tolerance. The applicability of this methodology was further highlighted by the late-stage modification of several natural products and pharmaceuticals. Article pubs.acs.org/joc

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Section: Introductionmentioning

confidence: 99%

Synthesis of Multisubstituted 2,3-Allenamides via Palladium-Catalyzed Carbonylation of Propargylic Esters

Zhang,

Ji,

et al. 2024

J. Org. Chem.

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“…Among these methods, transition-metal-catalyzed cross-coupling reactions, including the Pd- [ 7 ], Cu- [ 8 ], Zn- [ 9 ], Ni- [ 10 ], Mn- [ 11 ], Ag- [ 12 ], and Rh-catalyzed [ 13 ] phosphination reactions of various aryl partners with phosphine reagents, have received great attention [ 14 ]. In particular, researchers have focused on developing a mild, efficient, and environmentally benign method of C–P bond formation [ 15 , 16 , 17 ].…”

Section: Introductionmentioning

confidence: 99%

Metal-Free Phosphination and Continued Functionalization of Pyridine: A Theoretical Study

Yin

Dai

et al. 2022

Molecules

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This study investigates the mechanism of metal-free pyridine phosphination with P(OEt)3, PPh3, and PAr2CF3 using density functional theory calculations. The results show that the reaction mechanism and rate-determining step vary depending on the phosphine and additive used. For example, phosphination of pyridine with P(OEt)3 occurs in five stages, and ethyl abstraction is the rate-determining step. Meanwhile, 2-Ph-pyridine phosphination with PPh3 is a four-step reaction with proton abstraction as the rate-limiting step. Energy decomposition analysis of the transition states reveals that steric hindrance in the phosphine molecule plays a key role in the site-selective formation of the phosphonium salt. The mechanism of 2-Ph-pyridine phosphination with PAr2CF3 is similar to that with PPh3, and analyses of the effects of substituents show that electron-withdrawing groups decreased the nucleophilicity of the phosphine, whereas aryl electron-donating groups increased it. Finally, TfO− plays an important role in the C–H fluoroalkylation of pyridine, as it brings weak interactions.

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Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis

Tang,

Yang,

Han

et al. 2024

Angewandte Chemie

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Different from the reported work focusing on the construction of single P‐ or C‐stereocenter via hydrophosphinylation of unsaturated carbon bonds, the highly diastereo‐ and enantioselective hydrophosphinylation reaction of allenes, conjugated enynes and 1,3‐dienes is achieved via a designed Pd/Co dual catalysis and newly modified masked phosphinylating reagent. A series of allyl motifs bearing both a tertiary C‐ and P‐stereocenter are prepared in generally good yields, >20 : 1 dr, >20 : 1 rr and 99 % ee. The unprecedented diastereo‐ and enantioselective hydrophosphinylation of 1,3‐enynes is established to generate skeletons containing both a P‐stereocenter and a nonadjacent chiral axis. The first stereodivergent hydrophosphinylation reaction is also developed to achieve all four P‐containing stereoisomers. The present protocol features the use of only 3‐minutes reaction time and 0.1 % catalyst, and with the observation of up to 730 TON. A set of mechanistic studies reveal the necessity and roles of two metal catalysts and corroborate the designed synergistic process.

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Regio- and Stereoselective Addition of Secondary Phosphine Oxides to Allenoates Catalyzed by Main-Group Lewis Pairs

Cited by 13 publications

References 76 publications

Synthesis of Multisubstituted 2,3-Allenamides via Palladium-Catalyzed Carbonylation of Propargylic Esters

Synthesis of Multisubstituted 2,3-Allenamides via Palladium-Catalyzed Carbonylation of Propargylic Esters

Metal-Free Phosphination and Continued Functionalization of Pyridine: A Theoretical Study

Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis

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