Synthesis of 1-Oxadecalins from Anisole Promoted by Tungsten

The complex TpW(NO)(PMe3)(η2-anisole) is combined with acrolein or methyl vinyl ketone and various nucleophiles to generate novel chromen complexes. These complexes may be further elaborated by protonation and nucleophilic addition to generate chroman analogues with increased saturation and stereocenters. Treatment with various oxidants effects the decomplexation of the chromen

Synthesis of 1-Oxadecalins from Anisole Promoted by Tungsten

The complex TpW(NO)(PMe3)(η2-anisole) is combined with acrolein or methyl vinyl ketone and various nucleophiles to generate novel chromen complexes. These complexes may be further elaborated by protonation and nucleophilic addition to generate chroman analogues with increased saturation and stereocenters. Treatment with various oxidants effects the decomplexation of the chromen

Synthesis of 1-Oxadecalins from Anisole Promoted by Tungsten

The complex TpW(NO)(PMe3)(η2-anisole) is combined with acrolein or methyl vinyl ketone and various nucleophiles to generate novel chromen complexes. These complexes may be further elaborated by protonation and nucleophilic addition to generate chroman analogues with increased saturation and stereocenters. Treatment with various oxidants effects the decomplexation of the chromen

Single and Double Electrophilic Addition Reactions to the Aniline Ring Promoted by a Tungsten π-Base

Single and Double Electrophilic Addition Reactions to the Aniline Ring Promoted by a Tungsten π-Bas

Single and Double Electrophilic Addition Reactions to the Aniline Ring Promoted by a Tungsten π-Base

Single and Double Electrophilic Addition Reactions to the Aniline Ring Promoted by a Tungsten π-Bas

Synthesis of 1-Oxadecalins from Anisole Promoted by Tungsten

The complex TpW(NO)(PMe3)(η2-anisole) is combined with acrolein or methyl vinyl ketone and various nucleophiles to generate novel chromen complexes. These complexes may be further elaborated by protonation and nucleophilic addition to generate chroman analogues with increased saturation and stereocenters. Treatment with various oxidants effects the decomplexation of the chromen

Large-Scale Syntheses of Several Synthons to the Dearomatization Agent {TpW(NO)(PMe₃)} and Convenient Spectroscopic Tools for Product Analysis

A series of complexes of the form TpW(NO)(PMe3)(η2-arene) (where arene = benzene, anisole, dimethoxybenzene, trifluorotoluene, and naphthalene) are evaluated as practical synthons for the versatile dearomatization agent {TpW(NO)(PMe3)}, considering air stability, synthetic scalability, and substitution lability. Large-scale syntheses (9−30 g) are reported for several of these complexes as well as their precursors (TpW(NO)(CO2), TpW(NO)Br2, and TpW(NO)(PMe3)Br), and methods for spectroscopic characterization of composition and stereochemistry for the arene complexes (including JPW correlations) are summarized

Stereoelectronic Effects in Dihapto-Coordinated Complexes of TpW(NO)(PMe₃) and Their Manifestation in Diels−Alder Cycloaddition of Arenes

The addition of singly and doubly activated dienophiles to TpW(NO)(PMe3)(5,6-η2-anisole) and TpW(NO)(PMe3)(5,6-η2-1,3-dimethoxybenzene) to generate dihapto-coordinated [2.2.2]bicyclooctadienes and -trienes is explored. The highly functionalized bicyclic scaffolds are isolated from the metal fragment intact. Although moderate yields hinder their synthetic application, a unique stereoelectronic effect is uncovered. Coordination diastereomers of anisoles with the methoxy substituent distal to the PMe3 ligand have faster reaction rates relative to the proximal diastereomer. DFT calculations reveal the metal fragment possesses a dipole that directs positive charge away from the PMe3 ligand, and a polarized cycloaddition transition state is invoked to explain this observation

Stereoelectronic Effects in Dihapto-Coordinated Complexes of TpW(NO)(PMe₃) and Their Manifestation in Diels−Alder Cycloaddition of Arenes

The addition of singly and doubly activated dienophiles to TpW(NO)(PMe3)(5,6-η2-anisole) and TpW(NO)(PMe3)(5,6-η2-1,3-dimethoxybenzene) to generate dihapto-coordinated [2.2.2]bicyclooctadienes and -trienes is explored. The highly functionalized bicyclic scaffolds are isolated from the metal fragment intact. Although moderate yields hinder their synthetic application, a unique stereoelectronic effect is uncovered. Coordination diastereomers of anisoles with the methoxy substituent distal to the PMe3 ligand have faster reaction rates relative to the proximal diastereomer. DFT calculations reveal the metal fragment possesses a dipole that directs positive charge away from the PMe3 ligand, and a polarized cycloaddition transition state is invoked to explain this observation

Stereoelectronic Effects in Dihapto-Coordinated Complexes of TpW(NO)(PMe₃) and Their Manifestation in Diels−Alder Cycloaddition of Arenes

The addition of singly and doubly activated dienophiles to TpW(NO)(PMe3)(5,6-η2-anisole) and TpW(NO)(PMe3)(5,6-η2-1,3-dimethoxybenzene) to generate dihapto-coordinated [2.2.2]bicyclooctadienes and -trienes is explored. The highly functionalized bicyclic scaffolds are isolated from the metal fragment intact. Although moderate yields hinder their synthetic application, a unique stereoelectronic effect is uncovered. Coordination diastereomers of anisoles with the methoxy substituent distal to the PMe3 ligand have faster reaction rates relative to the proximal diastereomer. DFT calculations reveal the metal fragment possesses a dipole that directs positive charge away from the PMe3 ligand, and a polarized cycloaddition transition state is invoked to explain this observation