钯催化偶联（2010诺贝尔化学奖）.pdf.pdfVIP

Angewandte Chemie DOI: 10.1002/anie.201003764 Amination Palladium-Catalyzed Cross-Coupling of Aryl Chlorides and Tosylates with Hydrazine** Rylan J. Lundgren and Mark Stradiotto* Aryl hydrazines are highly valuable intermediates in the proceed rapidly under relatively mild conditions with excel- synthesis of a number of important nitrogen-containing lent monoarylation selectivity, thus providing direct access to heterocyclic frameworks such as indoles (through the Fischer aryl hydrazines. indole synthesis),[1] indazoles, aryl pyrazoles, and aryl tri- We began by screening a variety of ligands (Scheme 1) azoles.[2] In some cases, hydrazine reacts with haloarenes and reaction conditions (Table 1) in the hope of effecting the directly in nucleophilic aromatic substitution reactions; how- cross-coupling of 4-phenylchlorobenzene with readily avail- ever, such reactions typically occur at high temperatures, and/or only with highly electron-deficient haloarenes, or at [3, 4] Table 1: Optimization of the palladium-catalyzed cross-coupling of selected positions of halogenated heterocycles. The pre- 4-phenylchlorobenzene and N H ·H O.[a] 2 4 2 vailing method for the preparation of aryl hyd