Synthesis of P-chiral phosphines via chiral metal template promoted asymmetric furan Diels–Alder reaction

Yeo, Wee-Chuan; Chen, Shuli; Tan, Geok‐Kheng; Leung, Pak‐Hing

doi:10.1016/j.jorganchem.2007.02.041

Cited by 21 publications

(8 citation statements)

References 28 publications

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“…The asymmetric synthetic methodology adopted is illustrated in Scheme . The chloro ligand in complex R - 4a is well known to be kinetically and thermodynamically stable. , Therefore, it was removed by treatment of the complex with silver perchlorate to provide an easily accessible coordination site for the phosphrous donor atom. The chemically reactive intermediate perchlorato complex R - 5a was not isolated and was directly treated with 1 equiv of diphenylphosphine at −78 °C to give the desired hydrophosphination products.…”

Section: Resultsmentioning

confidence: 99%

“…Over the years, our group has prepared various functionalized chiral diphosphines with high stereoselectivity from a series of organopalladium-catalyzed asymmetric Diels−Alder reactions . Recently we found that the enantiomeric organopalladium complexes containing ( R )- and ( S )-(1-(dimethylamino)ethyl)naphthalene are also efficient promoters for hydrophosphination and hydroarsination reactions involving vinylic intermediates.…”

Section: Introductionmentioning

confidence: 99%

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Asymmetric Synthesis of Functionalized 1,2-Diphosphine via the Chemoselective Hydrophosphination of Coordinated Allylic Phosphines

Yuan

Pullarkat

et al. 2009

Organometallics

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Ester-and keto-functionalized allylic monophosphine palladium complexes containing ortho-metalated (R)-(1-(dimethylamino)ethyl)naphthalene as the chiral auxiliary were synthesized via a versatile one-pot process. Subsequent asymmetric hydrophosphination of the coordinated allylic substrates promoted by the chiral auxiliary gave the corresponding functionalized chiral 1,2-bis(diphenylphosphino)ethane ligands in high yields under mild conditions. The coordination properties and absolute configurations of the resultant diphosphine ligands were established by single-crystal X-ray crystallography. The coordinated 1,2-diphosphine ligands could be subsequently liberated stereospecifically to yield enantiomerically pure functionalized diphosphines in high yields.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Asymmetric Synthesis of Functionalized 1,2-Diphosphine via the Chemoselective Hydrophosphination of Coordinated Allylic Phosphines

Yuan

Pullarkat

et al. 2009

Organometallics

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“…Hence, after 7 days at rt, a mixture of 3 chelating diphosphines was obtained [128]. The same Pt precursor also allowed the formation of other optically pure cycloadducts, obtained after reaction between DPVP and 2-furyldiphenylarsine [129] or 2-diphenylphosphinofurane [130], or between PDVP and 2-diphenylphosphinofurane [131]. In the latter case, the control of the configuration of the chiral phosphorus atom is however lower than in the studies mentioned above since a 2:1 S P :R P ratio is obtained [131].…”

Section: Reactivity In Cycloaddition Reactionsmentioning

confidence: 95%

Alkenylphosphines: Applications in Synthesis, Catalysis and Coordination Chemistry

Julienne¹,

Toulgoat²,

Delacroix

et al. 2010

COC

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Alkenylphosphines are compounds of great interest in view of their structures. The most interesting feature is the carboncarbon double bond, which is directly linked to the phosphorus atom. Nucleophilic addition or cycloaddition reactions can take place at this unsaturation, which can also be used as a coordinating part in the presence of a metal. Thus, alkenylphosphines have found numerous applications in various fields of chemistry. They are useful intermediates in organic synthesis: numerous studies are devoted to their transformation into bidentate ligands, to their use as precursors for dendrimer and polymer chemistry or as ligand for homogeneous catalysis. Due to the presence of both the phosphorus atom and the carbon-carbon double bond, they are also of great interest in coordination chemistry and their different bonding modes have been largely documented. Moreover, after complexation to transition metal, a great amount of work has been carried out on their reactivity in cycloaddition reactions, as well as in functionalization of the carbon-carbon double bond and other miscellaneous reactions. These main applications will be reviewed hereafter.

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“…For example, the palladium or platinum complexes containing 1-(dimethylamino)ethylnaphthalene as auxiliary promoted the Diels−Alder reaction between dialkenylphenylphosphine with DMPP (3,4-dimethyl-1-phenylphosphole) to incorporate one of the alkene moieties into the bicyclo[2.2.1] group, thus generating a stereogenic center at phosphorus . In our group's previous works, palladium and platinum complexes promoted [4+2] ,, and [2+2] cycloaddition, hydrophosphination, hydroarsination, and hydroamination have been developed for the asymmetrical synthesis of chiral phosphines. Among these reactions, the above strategy, viz., functionalization of one unsaturated carbon−carbon bond of dialkenylphenylphosphines or dialkynylphenylphosphines, was often utilized in order to generate a stereogenic phosphorus.…”

Section: Introductionmentioning

confidence: 99%

Syntheses of Bimetallic Zwitterionic Complexes Containing Stereogenic Bifunctionalized Phosphine through Stepwise Insertion and Hydration Reactions

Luo

Pullarkat

et al. 2010

Organometallics

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A class of bifunctionalized phosphine complexes bearing a stereogenic center at phosphorus have been synthesized through stepwise insertion and hydration of the two alkynyl groups of a prochiral dialkynylphosphine complex, [Ru(η 6 -benzene){PPh(CtCCH 3 ) 2 }Cl 2 ]. One of the two alkyne moieties of this complex inserted into the Pd-C bond of cyclopalladated benzylamine complexes to yield bimetallic complexes containing two stereogenic centers at ruthenium and phosphorus with high stereoselectivity and yield. Subsequently, the remaining free alkynyl group underwent hydration in a mixed solvent system of DCM/acetone/H 2 O (2:10:1), which resulted in the formation of bimetallic zwitterions bearing anionic palladium(II) and cationic ruthenium(II) centers. The carbon-carbon triple bond was converted into a ketonyl group during the hydration, and the absolute configuration at phosphorus was observed to remain unchanged in the products. All structures of the insertion and hydration products have been identified by X-ray analyses or 2D ROESY NMR studies.

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Synthesis of P-chiral phosphines via chiral metal template promoted asymmetric furan Diels–Alder reaction

Cited by 21 publications

References 28 publications

Asymmetric Synthesis of Functionalized 1,2-Diphosphine via the Chemoselective Hydrophosphination of Coordinated Allylic Phosphines

Asymmetric Synthesis of Functionalized 1,2-Diphosphine via the Chemoselective Hydrophosphination of Coordinated Allylic Phosphines

Alkenylphosphines: Applications in Synthesis, Catalysis and Coordination Chemistry

Syntheses of Bimetallic Zwitterionic Complexes Containing Stereogenic Bifunctionalized Phosphine through Stepwise Insertion and Hydration Reactions

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