Spirocyclic and Bicyclic Cyclohexadienyl Complexes from Intramolecular Nucleophilic Addition Reactions in Dicationic Arene Complexes

Chae, Hyun Sik; Burkey, David J.

doi:10.1021/om030020k

Cited by 9 publications

(4 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As part of continuing studies aimed at further defining the synthetic potential of (η 6 -arene)RuCp + complexes, we have uncovered a general route for the preparation of novel cyclohexadienyl azaspirocyclic ruthenium complexes 2 from the corresponding N -benzyl acetoacetamide derivatives 1 (Scheme ). , The spirocyclic framework present in 2 exhibits an intriguing 2-azabicyclo[4.5]decane ring system that potentially offers numerous opportunities for stereocontrolled access to a range of derivatives, provided that suitable methods for removal of the CpRu fragment can be developed. Furthermore, cleavage of the cyclohexadienyl-Ru coordination without disruption of the spirocyclic linkage would complete a net Ru-mediated dearomatization of the benzylamine precursors.…”

Section: Introductionmentioning

confidence: 99%

Functionalized Spiro- and Fused-Ring Heterocycles via Oxidative Demetalation of Cyclohexadienyl Ruthenium Complexes

2004

View full text Add to dashboard Cite

Electron-rich alkoxy- and chloro-substituted azaspirocyclic cyclohexadienyl Ru(II) complexes have been converted to either azaspiro[4.5]decane derivatives or functionalized tetrahydroisoquinolines by treatment with suitable oxidizing agents. Copper(II) chloride was found to provide demetalated products in high yield relative to the other oxidants examined (FeCl(3), DDQ, CAN, [Cp(2)Fe][PF(6)], phenyliodine diacetate, IBX). In certain instances, the efficiency of oxidative demetalation was enhanced by the inclusion of chloride ion additives in the reaction. Pyridinium dichromate (PDC) was also found to effect the demetalation of a wide range of cyclohexadienyl Ru complexes; however, isolated yields of metal-free products were exceedingly low. The cyclohexadienyl ruthenium complexes used in this study were prepared from (arene)Ru(II) precursors; thus, the isolation of alicyclic cyclohexadienone derivatives upon demetalation constitutes completion of a Ru-mediated dearomatization process.

show abstract

Section: Introductionmentioning

confidence: 99%

Functionalized Spiro- and Fused-Ring Heterocycles via Oxidative Demetalation of Cyclohexadienyl Ruthenium Complexes

2004

View full text Add to dashboard Cite

show abstract

“…Specifically, the methylene carbon lies ~0.63 Å above the unsaturated ring, and the Fe atom is 1.60 Å away from the plane of this ring, analogously to the corresponding values (~0.65 and 1.66 Å) reported by Shirin, et al for a Ru-coordinated cyclohexadienyl ring [ 25 ]. The dihedral angle between the plane of the five carbons and the second plane of the three carbons that contains the saturated carbon is 45°, which is slightly larger but analogous to the 40° recorded for the (2-methoxycyclohexadienyl)Fe(CO) 3 + species [ 26 ]. The Fe-CF 3 bond of 1.968(3) Å, which very similar to the Fe-CF 3 of one of the few iron trifluoromethyl structures Fe[(CF 3 )(CON i Pr 2 )(CO 2 )(PPh 3 )], which is 1.979(4) Å [ 16 ].…”

Section: Resultsmentioning

confidence: 58%

Synthesis, Characterization, and X-ray Crystallography, of the First Cyclohexadienyl Trifluoromethyl Metal Complex (η5-C6H7)Fe(CO)2CF3

Douvris

Matatov²,

Bussan³

et al. 2022

Molecules

View full text Add to dashboard Cite

Fluorochemistry is a field of tremendous developments and advances in several areas of science including materials, pharmaceuticals and agriculture. This makes the design and synthesis of fluorine-containing substances highly desirable research targets. The sub-area of synthetic perfluorinated chemistry proportionately attracts widespread interest by applying to all areas of chemistry including organic and inorganic. Particularly, the latter is much underdeveloped as metal complexes with perfluoroalkyl moieties are scarce, with the vast majority of perfluorinated analogs, of long known, halo and alkylated derivatives never having been synthesized. Focusing on the chemistry of trifluoromethyl group, which is the most important in the class of perfluoroalkyls, we set out to explore the possibility of synthesizing and completely characterizing a cyclohexadienyl metal complex. Upon utilizing a number of trifluorometylating reagents, we only arrived at an efficient preparation by the use of Morrison’s trifluormethylating reagent. As a result, the new, air- and moisture-sensitive complex (η5-C6H7)Fe(CO)2CF3, was prepared in 71% yield, using a nucleophilic iodo-for-trifluoromethyl substitution, and was completely characterized including by X-ray crystallography.

show abstract

“…Not unexpectedly, nucleophilic addition to aryl ethers is practically unfeasible unless the ring charge density increase caused by the ether moiety is compensated by binding electron-withdrawing substituents to the aromatic system. Two representative examples of the activation of these aryl ethers toward nucleophilic attack are the complexation with electrophilic transition metal groups , and the incorporation of nitro groups into the ring (see section 14.1) . A particular dearomatization of an unactivated aryl ether was observed in the lithiation of 92 with tert -butyl-lithium (Scheme ).…”

Section: Aryl Ethersmentioning

confidence: 99%

Nucleophilic Dearomatizing (D_NAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis

et al. 2007

View full text Add to dashboard Cite

Institute fu ¨r Kohlenforschung (Mu ¨lheim a.d. Ruhr) with R. Benn investigating 187 Os NMR. In November 1989 he became Profesor Titular at the University of Oviedo, where he started his own research. He moved to the University of Almerı ´a (1996), where he is Professor of Organic Chemistry. His current research activities range from the application of phosphorus-stabilized carbanions in organic and organometallic chemistry to mechanistic studies of reactions involving organometallic species through multinuclear magnetic resonance. G. Ruiz Go ´mez was born in Madrid, Spain. She studied chemistry at the University of Almerı ´a and completed her first degree (Licenciatura) in July 2000. She was awarded a Ph.D. in 2006 for work on dearomatizing reactions of phosphinamides and phosphonamides under the direction of Professor Lo ´pez Ortiz. She is currently a postdoctoral fellow in Professor Lo ´pez-Ortiz's group with interest in the synthesis of non-natural peptides and peptide analogues.

show abstract

Spirocyclic and Bicyclic Cyclohexadienyl Complexes from Intramolecular Nucleophilic Addition Reactions in Dicationic Arene Complexes

Cited by 9 publications

References 17 publications

Functionalized Spiro- and Fused-Ring Heterocycles via Oxidative Demetalation of Cyclohexadienyl Ruthenium Complexes

Functionalized Spiro- and Fused-Ring Heterocycles via Oxidative Demetalation of Cyclohexadienyl Ruthenium Complexes

Synthesis, Characterization, and X-ray Crystallography, of the First Cyclohexadienyl Trifluoromethyl Metal Complex (η5-C6H7)Fe(CO)2CF3

Nucleophilic Dearomatizing (D_NAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis

Contact Info

Product

Resources

About

Spirocyclic and Bicyclic Cyclohexadienyl Complexes from Intramolecular Nucleophilic Addition Reactions in Dicationic Arene Complexes

Cited by 9 publications

References 17 publications

Functionalized Spiro- and Fused-Ring Heterocycles via Oxidative Demetalation of Cyclohexadienyl Ruthenium Complexes

Functionalized Spiro- and Fused-Ring Heterocycles via Oxidative Demetalation of Cyclohexadienyl Ruthenium Complexes

Synthesis, Characterization, and X-ray Crystallography, of the First Cyclohexadienyl Trifluoromethyl Metal Complex (η5-C6H7)Fe(CO)2CF3

Nucleophilic Dearomatizing (DNAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis

Contact Info

Product

Resources

About

Nucleophilic Dearomatizing (D_NAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis