General N−H Activation of Primary Alkylamines by a Late Transition-Metal Complex

Driver, Michael S.; Hartwig, John F.

doi:10.1021/ja954129y

Cited by 68 publications

(43 citation statements)

References 25 publications

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“…The reaction of fPd(PPh 3 )(Ph)(m-OH)} 2 with primary alkylamines to generate palladium amido complexes and water (Eq. (49)) [70,280] gave an early indication that the conversion of an alkoxide to an amide could be occurring during the catalytic cycle. These reactions are reversible, but the equilibrium favors the amido complex.…”

Section: ð48þmentioning

confidence: 99%

Palladium‐Catalyzed Amination of Aryl Halides and Sulfonates

Hartwig

2002

Modern Arene Chemistry

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The transition metal catalyzed synthesis of arylamines by the reaction of aryl halides or triflates with primary or secondary amines has become a valuable synthetic tool for many applications. This process forms monoalkyl or dialkyl anilines, mixed diarylamines or mixed triarylamines, as well as N-arylimines, carbamates, hydrazones, amides, and tosylamides. The mechanism of the process involves several new organometallic reactions. For example, the CaN bond is formed by reductive elimination of amine, and the metal amido complexes that undergo reductive elimination are formed in the catalytic cycle in some cases by NaH activation. Side products are formed by b-hydrogen elimination from amides, examples of which have recently been observed directly. An overview that covers the development of synthetic methods to form arylamines by this palladium-catalyzed chemistry is presented. In addition to the synthetic information, a description of the pertinent mechanistic data on the overall catalytic cycle, on each elementary reaction that comprises the catalytic cycle, and on competing side reactions is presented. The review covers manuscripts that appeared in press before June 1, 2001. This chapter is based on a review covering the literature up to September 1, 1999. However, roughly one-hundred papers on this topic have appeared since that time, requiring an updated review.

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Section: ð48þmentioning

confidence: 99%

Palladium‐Catalyzed Amination of Aryl Halides and Sulfonates

Hartwig

2002

Modern Arene Chemistry

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“…[69] Die Spaltung von N-H-Bindungen in Alkylaminen durch späte Übergangsmetalle ist ebenfalls selten. [74,75] führen zu Übergangsmetall-Amidokomplexen. Diese sind im Fall der späten Übergangsmetalle hochreaktiv.…”

Section: Neuartige Metallorganische Chemieunclassified

Übergangsmetall-katalysierte Synthese von Arylaminen und Arylethern aus Arylhalogeniden und -triflaten: Anwendungen und Reaktionsmechanismus

Hartwig

1998

Angewandte Chemie

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Oxidative Addition und reduktive Eliminierung sind die zentralen Schritte bei neuen Pd‐katalysierten Reaktionen zur Bildung von C‐N‐ und C‐O‐Bindungen von Arylaminen bzw. ‐ethern. Im nebenstehenden Mechanismusvorschlag wird ein Amin durch reduktive Eliminierung aus einem vierfach koordinierten 16‐Elektronen‐Amidoarylkomplex gebildet. Die Verwendung eines chelatisierenden Liganden wie 1,1′‐Bis(diphenylphosphanyl)ferrocen (dppf) verringert dabei das Ausmaß der konkurrierenden β‐Wasserstoffeliminierung. X=Br, I; R, R′=Alkyl, Aryl.

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“…In case of tri-o-tolylphosphine the steric bulk leads to superior reactivity by favoring low coordination numbers at the metal center. Studies from the groups of Buchwald [13] and Hartwig [14] of late-transition metal amido complexes led to new second-generation aryl halide amination catalysts based on chelating bisphosphine ligands. While Hartwig used a 1,1 '-bis(dipheny1phosphino)ferrocene ligand Buchwald employed BINAP as ligand.…”

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confidence: 99%