PALLADIUM-CATALYZED AROMATIC AMINATION OF ARYL BROMIDES WITH N,N-DI-ETHYLAMINO-TRIBUTYLTIN

Abstract

The reaction of N,N-diethylamino-tributyltin with aryl bromides in the presence of a catalytic amount of PdCl2(o-tolyl3P)2 gave N,N-diethylaminobenzene derivatives. The reaction is a new kind of amination different from ones through aryne or SRN1 mechanise

Pd‐Catalyzed Aryl Amination Mediated by Well Defined, N‐Heterocyclic Carbene (NHC)–Pd Precatalysts, PEPPSI

“…In 1995, the groups of Buchwald [1] and Hartwig, [2] building on the earlier ground-breaking work of Kosugi, [3] independently reported the first Pd-catalyzed aminations of aryl bromides with free amines. [4] Since these seminal publications, the Buchwald-Hartwig amination reaction has been developed into a valuable synthetic tool.…”

Rhodium‐Catalyzed Direct CH Amination of Benzamides with Aryl Azides: A Synthetic Route to Diarylamines

“…The subsequent development of catalytic methods for this N-arylation has been predicated upon the choice of suitable ligands (Scheme 1 b). [6,7] In recent years, new research has been focused on metalcatalyzed direct C À H amination (or amidation) of (hetero)-arenes without the need for pre-functionalized aryl halides. [8] Although this approach is highly promising, it still generates stoichiometric amounts of by-products from the external oxidants, [9] halide salts, or bases employed; [10] the substrate scope is also often rather limited.…”

A Tuned Bicyclic Proazaphosphatrane for Catalytically Enhanced N‐Arylation Reactions with Aryl Chlorides

“…[2] In 1983, Migita and co-workers developed this N-arylation methodology for the coupling of Bu 3 SnNEt 2 with aryl bromides in the presence of PdCl 2 [P(oTol) 3 ] 2 (oTol = o-tolyl). [3] Significantly improved catalytic systems for N-arylation reactions have subsequently been developed by Buchwald, [4] Hartwig, [5] and others.…”

“…[2] In 1983, Migita and co-workers developed this N-arylation methodology for the coupling of Bu 3 SnNEt 2 with aryl bromides in the presence of PdCl 2 [P(oTol) 3 ] 2 (oTol = o-tolyl). [3] Significantly improved catalytic systems for N-arylation reactions have subsequently been developed by Buchwald, [4] Hartwig, [5] and others. [6] Organotin-free palladium-catalyzed N-arylation reactions of various amines with aryl halides in the presence of bulky bases such as tBuOK [5a] and lithium hexamethyldisilazide (LiHMDS) [7] were introduced by the Buchwald and Hartwig groups.…”