Nickel or Palladium‐Catalyzed Decarbonylative Transformations of Carboxylic Acid Derivatives

Abstract

Carboxylic acid derivatives containing acyl halides, anhydrides, esters, amides and acyl nitriles are highly appealing electrophiles in transition-metal-catalyzed carboncarbon bond-forming reactions due to their ready availability and low cost, which can provide divergent transformations of carboxylic acids into other value-added products. In this Minireview, we focus on the recent advances of decarbonylative transformations of carboxylic acid derivatives in carbon-carbon bond formations using Ni or Pd catalysts. A series of reaction types, product classifications and reaction pathways are presented herein, which show the advantageous features of carboxylic acid derivatives as alternative to aryl or alkyl halides in terms of reactivity and compatibility. The well-accepted mechanism of nickel-or palladiumcatalyzed decarbonylative transformations involves initial oxidative addition of carboxylic acid derivatives, followed by decarbonylation or transmetalation (or insertion), and reductive elimination to generate the products, thereby regenerating the catalysts. 2 3 4 5 6 7 8

Ni/Pd-catalyzed Suzuki–Miyaura cross-coupling of alcohols and aldehydes and C–N cross-coupling of nitro and aminesviadomino redox reactions: base-free, hydride acceptor-free

“…The coupling product is formed aer several intermediates and the catalyst returns to the cycle by removing B(OH) 2 (CH 2 OH). [27][28][29] Control experiments (Table 5) were performed to help understand this mechanism. Elimination of any of the catalytic centers ( Table 5, entries 1, 2, 8 and 9) and removal of oxygen ( Table 5, entry 10) caused the catalytic activity to stop.…”

Silver Catalyzed Decarbonylative [3 + 2] Cycloaddition of Cyclobutenediones and Formamides

“…Heating the reaction mixture at 170 °C in the absence of catalyst, no reaction occurred ( Table 1 , entry 1). Considering the wide catalytic applications of transition metals in carbonylation and/or decarbonylation reaction, rhodium [ 33 ] and palladium [ 34 ] salts were firstly adopted in our decarbonylative [3 + 2] cycloaddition. Fortunately, the reaction occurred under the rhodium catalyst [Cp*RhCl 2 ] 2 or Rh(PPh 3 ) 3 Cl (Entries 2 and 3).…”

Organometallic Gas‐phase Ion Chemistry and Catalysis: Insights Into the Use of Metal Catalysts to Promote Selectivity in the Reactions of Carboxylic Acids and Their Derivatives

“…The potential of metal-catalyzed decarbonylation of carboxylic acid derivatives for organic synthesis has attracted considerable renewed interest over the past decade as highlighted in several reviews (Dzik, Lange, & Goossen, 2012;Dermenci & Dong, 2013;Takise, Muto, & Yamaguchi, 2017;Guo & Rueping, 2018a,b;Wang, Wang, & Nishihara, 2020). Some representative transformations are shown in Scheme 7.…”