6742-54-7Relevant articles and documents
Merging Halogen-Atom Transfer (XAT) and Copper Catalysis for the Modular Suzuki-Miyaura-Type Cross-Coupling of Alkyl Iodides and Organoborons
Zhang, Zhenhua,Górski, Bartosz,Leonori, Daniele
supporting information, p. 1986 - 1992 (2022/02/01)
We report here a mechanistically distinct approach to achieve Suzuki-Miyaura-type cross-couplings between alkyl iodides and aryl organoborons. This process requires a copper catalyst but, in contrast with previous approaches based on palladium and nickel
Relevance of Single-Transmetalated Resting States in Iron-Mediated Cross-Couplings: Unexpected Role of σ-Donating Additives
Rousseau, Lidie,Touati, Nadia,Binet, Laurent,Thuéry, Pierre,Lefèvre, Guillaume
supporting information, p. 7991 - 7997 (2021/05/26)
Control of the transmetalation degree of organoiron(II) species is a critical parameter in numerous Fe-catalyzed cross-couplings to ensure the success of the process. In this report, we however demonstrate that the selective formation of a monotransmetalated FeII species during the catalytic regime counterintuitively does not alone ensure an efficient suppression of the nucleophile homocoupling side reaction. It is conversely shown that a fine control of the transmetalation degree of the transient FeIII intermediates obtained after the activation of alkyl electrophiles by a single-electron transfer (SET), achievable using σ-donating additives, accounts for the selectivity of the cross-coupling pathway. This report shows for the first time that both coordination spheres of FeII resting states and FeIII short-lived intermediates must be efficiently tuned during the catalytic regime to ensure high coupling selectivities.
Nickel-Catalyzed Decarboxylative Alkylation of Aryl Iodides with Anhydrides
Chen, Hui,Hu, Lu,Ji, Wenzhi,Yao, Licheng,Liao, Xuebin
, p. 10479 - 10485 (2018/10/24)
We present the anhydride-based decarboxylative alkylation of aryl iodides catalyzed by nickel. This method of decarboxylative coupling works with a broad scope of aliphatic carboxylic anhydrides and tolerates synthetically useful aromatic substituents. Assisted by a redox system of pyridine N-oxide and zinc additives, the current reaction occurs under mild conditions and without the assistance of photocatalyst. Notably, this method features high chemoselectivity toward alkyl migration with mixed aliphatic/aromatic anhydrides. Thus, it provides a powerful synthetic tool to modify high-valued aliphatic carboxylic acids by converting them into mixed anhydrides using readily available aryl carboxylic acids such as p-toluic acid. We propose a catalytic cycle that involves the key steps of free radical-based decarboxylation and subsequent alkyl transfer to nickel that precedes an oxidatively induced C-C reductive elimination from Ni(III).
