43008-84-0Relevant academic research and scientific papers
In-Situ Bromination Enables Formal Cross-Electrophile Coupling of Alcohols with Aryl and Alkenyl Halides
Chi, Benjamin K.,Widness, Jonas K.,Gilbert, Michael M.,Salgueiro, Daniel C.,Garcia, Kevin J.,Weix, Daniel J.
, p. 580 - 586 (2022/01/03)
Although alcohols are one of the largest pools of alkyl substrates, approaches to utilize them in cross-coupling and cross-electrophile coupling are limited. We report the use of 1° and 2° alcohols in cross-electrophile coupling with aryl and vinyl halides to form C(sp3)–C(sp2) bonds in a one-pot strategy utilizing a very fast (a 96-well plate.
Modular radical cross-coupling with sulfones enables access to sp3-rich (fluoro)alkylated scaffolds
Merchant, Rohan R.,Edwards, Jacob T.,Qin, Tian,Kruszyk, Monika M.,Bi, Cheng,Che, Guanda,Bao, Deng-Hui,Qiao, Wenhua,Sun, Lijie,Collins, Michael R.,Fadeyi, Olugbeminiyi O.,Gallego, Gary M.,Mousseau, James J.,Nuhant, Philippe,Baran, Phil S.
, p. 75 - 80 (2018/02/28)
Cross-coupling chemistry is widely applied to carbon-carbon bond formation in the synthesis of medicines, agrochemicals, and other functional materials. Recently, single-electron-induced variants of this reaction class have proven particularly useful in the formation of C(sp2)-C(sp3) linkages, although certain compound classes have remained a challenge. Here, we report the use of sulfones to activate the alkyl coupling partner in nickel-catalyzed radical cross-coupling with aryl zinc reagents. This method's tolerance of fluoroalkyl substituents proved particularly advantageous for the streamlined preparation of pharmaceutically oriented fluorinated scaffolds that previously required multiple steps, toxic reagents, and nonmodular retrosynthetic blueprints. Five specific sulfone reagents facilitate the rapid assembly of a vast set of compounds, many of which contain challenging fluorination patterns.
Acceleration of CuI-catalyzed coupling reaction of alkyl halides with aryl Grignard reagents using lithium chloride
Nakata, Kenya,Feng, Chao,Tojo, Toshifumi,Kobayashi, Yuichi
supporting information, p. 5774 - 5777 (2014/12/11)
In the presence of LiCl, CuI-catalyzed coupling reaction of R(alkyl)-X with Ar(aryl)MgBr at rt was completed within 2 h. Effective leaving groups X in R-X were Br, I, OTs, but not Cl. Grignard reagents ArMgBr with both standard and bulky Ar such as 2-MeC
A user-friendly, all-purpose Pd-NHC (NHC = N-heterocyclic carbene) precatalyst for the Negishi reaction: A step towards a universal cross-coupling catalyst
Organ, Michael G.,Avola, Stephanie,Dubovyk, Igor,Hadei, Niloufar,Kantchev, Eric Assen B.,O'Brien, Christopher J.,Valente, Gory
, p. 4749 - 4755 (2008/02/08)
We have developed the first user-friendly Negishi protocol capable of routinely cross-coupling all combinations of alkyl and aryl centers. The use of an easily synthesized, air stable, highly active, well-defined precatalyst PEPPSI-IPr (1; PEPPSI = pyridine-enhanced precatalyst preparation, stabilization and initiation; IPr = diisopropyl-phenylimidazolium derivative) substantially increases the scope, reliability, and ease-of-use of the Negishi reaction. All organohalides and routinely used pseudohalides were excellent coupling partners, with the use of chlorides, bromides, iodides, triflates, tosylates, and mesylates resulting in high yield of the coupled product. Furthermore, all reactions were performed by using general laboratory techniques, with no glove box necessary as the precatalyst was weighed and stored in air. Utilization of this methodology allowed for the easy synthesis of an assortment of sterically encumbered biaryls and druglike heteroaromatics, demonstrating the value of the PEPPSI-IPr system. Furthermore, this is also the first time Pd-NHC (NHC = N-heterocyclic carbene) methodology has surpassed the related phosphine-ligated Negishi processes both in activity and use.
