5 research outputs found

    Heck Alkynylation (Copper-Free Sonogashira Coupling) of Aryl and Heteroaryl Chlorides, Using Pd Complexes of <i>t</i>‑Bu<sub>2</sub>(<i>p</i>‑NMe<sub>2</sub>C<sub>6</sub>H<sub>4</sub>)P: Understanding the Structure–Activity Relationships and Copper Effects

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    L<sub>2</sub>Pd­(0) and L<sub>2</sub>Pd­(II) complexes, where L= <i>t</i>-Bu<sub>2</sub>(<i>p</i>-NMe<sub>2</sub>C<sub>6</sub>H<sub>4</sub>)­P, have been identified as efficient catalyst systems for the Heck alkynylation of a variety of aryl bromides (17 examples) and aryl/heteroaryl chlorides (31 examples) with a range of aryl- and alkyl-acetylenes in excellent yields, under relatively low Pd loadings. The single-crystal X-ray structure determination of the presumably active catalytic species, L<sub>2</sub>Pd­(0), was carried out in this study to better understand the superior activity of the current catalyst system from a structure–activity relationship point of view. The P–Pd–P bond angle indicates that the complex is bent (174.7°) in comparison to the perfectly linear (180.0°) structure of the analogous Pd­(<i>t</i>-Bu<sub>3</sub>P)<sub>2</sub>. Preliminary mechanistic studies on the negative copper effect and substrate effect of aryl acetylenes were conducted to better understand the cross-coupling pathway of Heck alkynylation

    Chiral Allene-Containing Phosphines in Asymmetric Catalysis

    No full text
    We demonstrate that allenes, chiral 1,2-dienes, appended with basic functionality can serve as ligands for transition metals. We describe an allene-containing bisphosphine that, when coordinated to Rh(I), promotes the asymmetric addition of arylboronic acids to α-keto esters with high enantioselectivity. Solution and solid-state structural analysis reveals that one olefin of the allene can coordinate to transition metals, generating bi- and tridentate ligands

    Chiral Allene-Containing Phosphines in Asymmetric Catalysis

    No full text
    We demonstrate that allenes, chiral 1,2-dienes, appended with basic functionality can serve as ligands for transition metals. We describe an allene-containing bisphosphine that, when coordinated to Rh(I), promotes the asymmetric addition of arylboronic acids to α-keto esters with high enantioselectivity. Solution and solid-state structural analysis reveals that one olefin of the allene can coordinate to transition metals, generating bi- and tridentate ligands

    Chiral Allene-Containing Phosphines in Asymmetric Catalysis

    No full text
    We demonstrate that allenes, chiral 1,2-dienes, appended with basic functionality can serve as ligands for transition metals. We describe an allene-containing bisphosphine that, when coordinated to Rh(I), promotes the asymmetric addition of arylboronic acids to α-keto esters with high enantioselectivity. Solution and solid-state structural analysis reveals that one olefin of the allene can coordinate to transition metals, generating bi- and tridentate ligands

    Chiral Allene-Containing Phosphines in Asymmetric Catalysis

    No full text
    We demonstrate that allenes, chiral 1,2-dienes, appended with basic functionality can serve as ligands for transition metals. We describe an allene-containing bisphosphine that, when coordinated to Rh(I), promotes the asymmetric addition of arylboronic acids to α-keto esters with high enantioselectivity. Solution and solid-state structural analysis reveals that one olefin of the allene can coordinate to transition metals, generating bi- and tridentate ligands
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