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
L<sub>2</sub>PdÂ(0) and L<sub>2</sub>PdÂ(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>)ÂP, 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>PdÂ(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 PdÂ(<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
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
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
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
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