The Hydroarylation Reaction—Scope and Limitations

Abstract

The synthetic potential of stereoselective, palladium-catalyzed hydro(het)arylation reactions of bi-, tri- and tetracyclic (hetero)alkenes in the presence of phospines and arsines as highly efficient ligands was studied. The mechanism of this reductive Heck reaction becomes more complex in the case of benzonorbornenes. Hydroarylation of diazabicyclo-[2.2.1]heptenes provides a stereoselective access to aryldiaminocyclopentanes. Electron-deficient arylpalladium complexes shift the reaction towards the product of a formal 1,2-hydrazidoarylation reaction of 1,3-cyclopentadiene by a stereoselective C-N cleavage. Due to steric reasons, rigid bicyclo[2.2.2]octenes react slower in hydroarylation reactions than the corresponding bicyclo[2.2.1]heptenes. The more flexible bicyclo[4.2.2]decene system already tends to undergo domino-Heck reactions, even under reductive conditions. When a tetracyclic cis-allylcyclopropane is carbopalladated in the presence of formates, the neighboring cyclopropane ring is attacked in the first reported example of a pi,sigma domino-Heck reaction.

Hydroarylation Reactions of N-Acylaminosubstituted Tricyclic Imides

“…The same reaction was performed with p-tert-butylbenzoyl chloride to give N- (4- (6). The tricyclic imide 4 also reacted with 3-methylisoxazole-5-carbonyl chloride to give N- (3-…”

In(III)-TMSBr-Catalyzed Cascade Reaction of Diarylalkynes with Acrylates for the Synthesis of Aryldihydronaphthalene Derivatives

“…Consequently, their significant roles have driven the establishment of several synthetic methodologies for their preparation. Prominently, the intramolecular hydroarylation of 4-phenyl-1-butyne or its derivatives is one of the most versatile protocols for the construction of aryldihydronaphthalene derivatives [ 12 , 13 , 14 , 15 ]. Since the pioneering studies by Fujiwara et al [ 16 , 17 ], numerous catalytic methods have been developed in this field in which a series of transition metals, Lewis and Bronsted acids have been found effective for catalyzing the hydroarylation [ 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 ].…”

Synthesis of 3-Substituted Pyrrolidines via Palladium-Catalyzed Hydroarylation

“…In theory, interception of 1 and 5 by a hydride source could lead to saturated products, rather than alkenes; in practice, such hydroarylation reactions ( Beletskaya and Cheprakov, 2000 , Namyslo et al., 2010 ) are narrowly confined to conjugate-like additions ( Figure 3 A) ( Cacchi and Arcadi, 1983 ), constrained alkenes ( Larock and Johnson, 1989 , Bai et al., 1996 ), and intramolecular processes ( Figure 3 B) ( Larock and Babu, 1987 , Burns et al., 1988 , Kong et al., 2017 , Diethelm and Carreira, 2015 ). Although a rhodium-catalyzed process has been reported ( Figure 3 C) ( So et al., 2013 ), to date, only one intermolecular palladium-catalyzed hydroarylation reaction to give pyrrolidines has been described ( Figure 3 D) ( Gurak and Engle, 2018 ); we report here a novel, broad-scope, palladium-catalyzed hydroarylation process ( Figure 3 E), directly furnishing 3-substituted pyrrolidines efficiently.…”