2,2'-Bipyridyls have been utilized as indispensable ligands in metal-catalyzed reactions.T he most streamlined approach for the synthesis of 2,2'-bipyridyls is the dehydrogenative dimerization of unfunctionalized pyridine.H erein, we report on the palladium-catalyzed dehydrogenative synthesis of 2,2'-bipyridyl derivatives.The Pd catalysis effectively works with an Ag I salt as the oxidant in the presence of pivalic acid. A variety of pyridines regioselectively react at the C2-positions. This dimerization method is applicable for challenging substrates such as sterically hindered 3-substituted pyridines, where the pyridines regioselectively react at the C2-position. This reaction enables the concise synthesis of twisted 3,3'disubstituted-2,2'-bipyridyls as an underdeveloped class of ligands.
Herein, we report on the first enantioselective and atom-efficient catalytic one-step dimerization method to selectively transform ω-allenyl carboxylic acids into C -symmetric 14- to 28-membered bismacrolactones (macrodiolides). This convenient asymmetric access serves as an attractive route towards multiple naturally occuring homodimeric macrocyclic scaffolds and demonstrates excellent efficiency to construct the complex, symmetric core structures. By utilizing a rhodium catalyst with a modified chiral cyclopentylidene-diop ligand, the desired diolides were obtained in good to high yields, high diastereoselectivity, and excellent enantioselectivity.
A short and efficient synthesis of the C2‐symmetric antibiotic (−)‐vermiculine by utilizing an enantioselective catalytic one‐step dimerization methodology as key‐step to construct the core structure is reported. The late‐stage modifications feature a double metathesis homologation followed by a double Wacker‐type oxidation. These key‐steps allowed the synthesis of vermiculine in only seven steps, starting from commercially available building blocks.
2,2'-Bipyridyls have been utilized as indispensable ligands in metal-catalyzed reactions.T he most streamlined approach for the synthesis of 2,2'-bipyridyls is the dehydrogenative dimerization of unfunctionalized pyridine.H erein, we report on the palladium-catalyzed dehydrogenative synthesis of 2,2'-bipyridyl derivatives.The Pd catalysis effectively works with an Ag I salt as the oxidant in the presence of pivalic acid. A variety of pyridines regioselectively react at the C2-positions. This dimerization method is applicable for challenging substrates such as sterically hindered 3-substituted pyridines, where the pyridines regioselectively react at the C2-position. This reaction enables the concise synthesis of twisted 3,3'disubstituted-2,2'-bipyridyls as an underdeveloped class of ligands.
Herein, we report on the first enantioselective and atom-efficient catalytic one-step dimerization method to selectively transform w-allenyl carboxylic acids into C 2 -symmetric 14-to 28-membered bismacrolactones (macrodiolides). This convenient asymmetric access serves as an attractive route towards multiple naturally occuring homodimeric macrocyclic scaffolds and demonstrates excellent efficiency to construct the complex, symmetric core structures.B yu tilizing ar hodium catalyst with am odified chiral cyclopentylidene-diop ligand, the desired diolides were obtained in good to high yields,high diastereoselectivity,and excellent enantioselectivity.
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