Synthesis and Structural Characterization of a Series of New Chiral‐at‐Metal Ruthenium Allenylidene Complexes

Costin, Stephen; Widaman, Andria K.; Rath, Nigam P.; Bauer, Eike B.

doi:10.1002/ejic.201001176

Cited by 15 publications

(20 citation statements)

References 123 publications

(66 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The precursor complex [RuCl(ind)(PPh 3 ) 2 ] has been used as a starting material for the syntheses of ruthenium complex through ligand‐substitution reactions by us13,15e,15f and others 22. Accordingly, when [RuCl(ind)(PPh 3 ) 2 ] was heated with 1.1 equiv.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structural Characterization, and Catalytic Activity of Indenyl Tris(N‐pyrrolyl)phosphine Complexes of Ruthenium

et al. 2016

Self Cite

View full text Add to dashboard Cite

The synthesis, characterization, and catalytic activity of new ruthenium complexes of the tris(N-pyrrolyl)phosphine ligand [P(pyr) 3 ] are described. The new ruthenium complexes [RuCl(ind)(PPh 3 ){P(pyr) 3 }] and [RuCl(ind){P(pyr) 3 } 2 ] (ind = indenyl, η 5 -C 9 H 7 -) were synthesized in 73 and 63 % isolated yields, respectively, by thermal ligand exchange of [RuCl(ind)(PPh 3 ) 2 ] with P(pyr) 3 . The electronic and steric properties of the new complexes were studied through analysis of the X-ray structures and cyclic voltammetry. The new complexes [RuCl(ind)(PPh 3 )-{P(pyr) 3 }] and [RuCl(ind){P(pyr) 3 } 2 ] and the known complex [RuCl(ind){(PPh 3 ) 2 }] differed only slightly in their steric proper-[a]

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis, Structural Characterization, and Catalytic Activity of Indenyl Tris(N‐pyrrolyl)phosphine Complexes of Ruthenium

et al. 2016

Self Cite

View full text Add to dashboard Cite

show abstract

“…The commercial propargyic alcohol HCCC(OH)(t-Bu)(2naphthyl) (9) seemed to be a good starting material for the synthesis of a corresponding allenylidene complex. Following a protocol previously established in our laboratory, 33 the chloro precursor complex (R Ru ,R ax )-7 was first treated with (Et 3 O)PF 6 to selectively remove the chloro ligand (Scheme 2). Upon addition of the propargylic alcohol 9,…”

Section: ■ Resultsmentioning

confidence: 99%

“…33 The complex was converted to a series of ruthenium allenylidene complexes of the formula (R Ru ,R ax )-[Ru(Ind)(PPh 3 )(6)(C CCR 1 R 2 )] + PF 6 − (R 1 /R 2 = Ph/Ph, Ph/Me, Me/2-furyl) with complete retention of configuration at the stereogenic ruthenium center. 33 We hypothesized that these allenylidene complexes would be good candidates to investigate the stereoselectivity of nucleophilic attack. Herein, we present a new chiral-at-metal allenylidene complex, (R Ru ,R ax )-[Ru(Ind)-(PPh 3 )(6){CCC(t-Bu)(2-naphthyl)}] + PF 6 − .…”

Section: ■ Introductionmentioning

confidence: 99%

Diastereoselective Attack on Chiral-at-Metal Ruthenium Allenylidene Complexes To Give Alkynyl Complexes

2014

Self Cite

View full text Add to dashboard Cite

New chiral ruthenium(II) allenylidene complexes were synthesized, and their reactivity with nucleophiles to give alkynyl complexes was investigated. The new allenylidene complex (R Ru ,R ax )-[Ru(Ind)(PPh 3 )(6){C CC(t-Bu)(2-naphthyl)}] + PF 6 − was synthesized from the chloro precursor complex (R Ru ,R ax )-[RuCl(Ind)(PPh 3 )( 6)] and the racemic propargylic alcohol HCCC(OH)(t-Bu)(2naphthyl) and obtained in 96% yield, where (R ax )-6 is a chiral phosphoramidite and Ind an anionic indenyl ligand. The precursor and the allenylidene complex are chiral-at-metal, and the chiral information is completely transferred from the chloro precursor to the product allenylidene complex, both of which show the same absolute configuration, as demonstrated by X-ray diffraction. Together with the known allenylidene complex (R Ru ,R ax )-[Ru(Ind)(PPh 3 )(6)(CCCPh 2 )] + PF 6 − , the attack of n-BuLi, MeLi, LiCCPh, and lithium 1-phenylethenolate nucleophiles on the allenylidene chain of (R Ru ,R ax )-[Ru(Ind)(PPh 3 )-( 6){CCC(t-Bu)(2-naphthyl)}] + PF 6 − was investigated. The nucleophiles (Nu) reacted selectively with the gamma carbon of the allenylidene complexes to give the alkynyl complexes (R Ru ,R ax )-[Ru(Ind)(PPh 3 )(6)(CC−CPh 2 Nu)] and (R Ru ,R ax )-[Ru(Ind)(PPh 3 )(6){CC−C(t-Bu)(2-naphthyl)Nu}] in 40% to 96% isolated yields. In the case of (R Ru ,R ax )-[Ru(Ind)(PPh 3 )-(6){CC−C*(t-Bu)(2-naphthyl)Nu}], the gamma carbon C* becomes stereogenic upon attack of the nucleophiles. As assessed by 31 P{ 1 H} NMR, diastereodifferentiation took place, and the alkynyl complexes were isolated as diastereomeric mixtures with diastereomeric ratios between 60:40 and 84:16. The diastereodifferentiation originated only from the stereogenic metal center and the monodentate, chiral ligand. The study allows for investigation of stereoselective, nucleophilic attack of allenylidene complexes to give optically active, quaternary alkynes, which play a role in potential catalytic versions of nucleophilic substitution reactions of propargylic alcohols.

show abstract

“…The presence of a base is usually needed to achieve good yields of the target compounds. Typical examples include the synthesis of proline derivative 1 (Scheme 1, A) 34 and the phosphorylation of 2,5-disubstituted pyrrolidine 2 with 2-chlorobenzo- [35][36][37] using triethylamine as the hydrochloric acid scavenger (Scheme 1, B). Inert solvents, such as THF 35,36 or diethyl ether 34,37 may be used, the former providing better yields.…”

Section: Synthesis Of Pyrrolidine-based P(iii) Derivativesmentioning

confidence: 99%

N-Phosphorylated Pyrrolidines: An Overview of Synthetic Approaches

et al. 2020

View full text Add to dashboard Cite

Organophosphorus pyrrolidine derivatives possessing P–N bonds are a promising yet underexplored class of compounds. In this short review we overview the general approaches to these compounds described so far, with a special emphasis on their asymmetric synthesis.1 Introduction2 Synthesis of Pyrrolidine-Based P(III) Derivatives3 Synthesis of Pyrrolidine-Based P(V) Derivatives3.1 Phosphorylation of Pyrrolidines with P(V) Acid Chlorides3.2 Phosphorylation of Pyrrolidines with P(V) Acid Esters3.3 Syntheses via the Atherton–Todd Reaction3.4 Oxidation of Pyrrolidine-Based P(III) Derivatives4 Syntheses of N-Phosphorylpyrrolidines from Acyclic Precursors5 Conclusions

show abstract

Synthesis and Structural Characterization of a Series of New Chiral‐at‐Metal Ruthenium Allenylidene Complexes

Abstract: New chiral-at-metal ruthenium indenyl PPh 3 phosphoramidite allenylidene complexes have been synthesized and structurally characterized. Through thermal ligand-exchange reactions with [RuCl(Ind)(PPh 3 ) 2 ], the phosphoramidite ligands

Cited by 15 publications

References 123 publications

Synthesis, Structural Characterization, and Catalytic Activity of Indenyl Tris(N‐pyrrolyl)phosphine Complexes of Ruthenium

Synthesis, Structural Characterization, and Catalytic Activity of Indenyl Tris(N‐pyrrolyl)phosphine Complexes of Ruthenium

Diastereoselective Attack on Chiral-at-Metal Ruthenium Allenylidene Complexes To Give Alkynyl Complexes

N-Phosphorylated Pyrrolidines: An Overview of Synthetic Approaches

Contact Info

Product

Resources

About