- Pd-Catalyzed Etherification of Nitroarenes
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The Pd-catalyzed etherification of nitroarenes with arenols has been achieved using a new rationally designed ligand. Mechanistic insights were used to design the ligand so that both the oxidative addition and reductive elimination steps of a plausible catalytic cycle were facilitated. The catalytic system established here provides direct access to a range of unsymmetrical diaryl ethers from nitroarenes.
- Matsushita, Naoki,Kashihara, Myuto,Formica, Michele,Nakao, Yoshiaki
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supporting information
p. 2209 - 2214
(2021/07/20)
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- An improved synthesis of brettphos- and rockphos-type biarylphosphine ligands
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Improved processes for the preparation of biphenyl-based phosphine ligands t-BuBrettPhos, RockPhos, and BrettPhos are presented. The new methods, featuring the use of Grignard reagents and catalytic amounts of copper, are superior to the previous methods, which require the use of tert-butyllithium and stoichiometric amounts of copper. Specifically, the use of less dangerous reagents provides a safer process, while the use of catalytic amounts of copper allows for the isolation of pure products in high yield. These improvements are particularly significant for the large-scale preparation of these ligands. Copyright
- Hoshiya, Naoyuki,Buchwald, Stephen L.
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experimental part
p. 2031 - 2037
(2012/10/08)
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- Evidence for in situ catalyst modification during the Pd-catalyzed conversion of aryl triflates to aryl fluorides
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A mechanistic investigation of the Pd-catalyzed conversion of aryl triflates to fluorides is presented. Studies reveal that C-F reductive elimination from a LPdII(aryl)F complex (L = t-BuBrettPhos or RockPhos) does not occur when the aryl group is electron rich. Evidence is presented that a modified phosphine, generated in situ, serves as the actual supporting ligand during catalysis with such substrates. A preliminary study of the reactivity of a LPdII(aryl)F complex based on this modified ligand is reported.
- Maimone, Thomas J.,Milner, Phillip J.,Kinzel, Tom,Zhang, Yong,Takase, Michael K.,Buchwald, Stephen L.
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scheme or table
p. 18106 - 18109
(2012/01/02)
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- A single phosphine ligand allows palladium-catalyzed intermolecular C-O bond formation with secondary and primary alcohols
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Forging a bond: An efficient, general palladium catalyst for C-O bond-forming reactions of secondary and primary alcohols with a range of aryl halides has been developed using the ligand 1. Heteroaryl halides, and for the first time, electron-rich aryl halides can be coupled with secondary alcohols. A diverse set of substrate combinations are possible with just a single ligand, thus obviating the need to survey multiple ligands. Copyright
- Wu, Xiaoxing,Fors, Brett P.,Buchwald, Stephen L.
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p. 9943 - 9947
(2011/12/05)
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