Divergent Reaction of Isocyanides with o-Bromobenzaldehydes: Synthesis of Ketenimines and Lactams with Isoindolinone Cores

Abstract

A divergent reaction of isocyanides with o-bromobenzaldehydes for the synthesis of isoindolinone-derived ketenimines and lactams was disclosed. The reaction features readily available reactants, relatively mild conditions, and high yields of products. Ketenimines could be applied in further transformations for access to other functional molecules. A mechanism study showed that the palladium-migration/imine-insertion process was the key step in this reaction.

Regiodivergent C–N Coupling of Quinazolinones Controlled by the Dipole Moments of Tautomers

“…4−7 Various metal-catalyzed divergent reactions for the synthesis of heterocyclic scaffolds were well explored. 8,9 Similarly, Pdand Cu-catalyzed annulative π-extension and N-arylation of unmasked 2-phenylquinazolin-4(3H)-ones were achieved in the presence of iodonium salts. 10 In this context, Du and coworkers reported the PhI(OCOOCF 3 ) 2 -or PIFA-mediated divergent synthesis of spiro [4,5]trienones and iodinated quinilin-2-ones from N-arylpropynamides, where PIFA acted as an iodination reagent and an oxidant.…”

Divergent Conversion of Double Isocyanides with Alkenyl Bromide to Polysubstituted Pyrroles and 4-Imino-4,5-dihydropyrrolo[3,4-b]pyrrol-6(1H)-one Derivatives by Pd-Catalyzed Tandem Cyclization Reactions

“…17 Thereafter, an ingenious work to generate two kinds of heterocyclic molecules controlled by diverse bases was reported by Ji's group (Scheme 1b). 18 Both results were initiated by alkyl or aryl halides with isocyanides. Inspired by the above works, we envisaged employing alkenyl bromide and isocyanide to explore more challenging double isocyanide reactions in heterocycle synthesis.…”

“…Recently, Jiang’s group disclosed a flexible reaction applying isocyanide and propargylic carbonates as the substrates to afford totally different molecular structures that could be modulated through different reaction conditions (Scheme a) . Thereafter, an ingenious work to generate two kinds of heterocyclic molecules controlled by diverse bases was reported by Ji’s group (Scheme b) . Both results were initiated by alkyl or aryl halides with isocyanides.…”

Porous Organophosphine Ligand Polymers as Recyclable Ligands for the Synthesis of Isoindolinone Compounds

“…把制备的 Pd/POL-PPh 3 作为 多相催化剂, 催化邻溴苯甲醛(1a)与叔丁基异腈(2a)的 反应, 以 98%的产率获得目标产物(Scheme 1, c), 同时 在标准条件下, 进行了均相金属钯/配体的实验, 结果以 68%的产率获得目标产物(Scheme 1, d). 与标准条件下 的均相金属钯/配体催化以及参考文献相比 [25] , 多相 Pd/POL-PPh 3 以更高的产率获得异吲哚啉酮类化合物, 而且 POL-PPh 3 可重复使用, 这不仅降低了反应的成本, 而且为合成异吲哚啉酮类化合物提供有趣的补充. 1.5 可能的反应机制 根据实验结果及已报道的文献 [25] , 推测了该反应 的机理(Scheme…”

“…与标准条件下 的均相金属钯/配体催化以及参考文献相比 [25] , 多相 Pd/POL-PPh 3 以更高的产率获得异吲哚啉酮类化合物, 而且 POL-PPh 3 可重复使用, 这不仅降低了反应的成本, 而且为合成异吲哚啉酮类化合物提供有趣的补充. 1.5 可能的反应机制 根据实验结果及已报道的文献 [25] , 推测了该反应 的机理(Scheme…”