1441122-89-9Relevant academic research and scientific papers
Base-Activated Latent Heteroaromatic Sulfinates as Nucleophilic Coupling Partners in Palladium-Catalyzed Cross-Coupling Reactions
Blakemore, David C.,Cook, Xinlan A. F.,Moses, Ian B.,Pantaine, Lo?c R. E.,Sach, Neal W.,Shavnya, Andre,Willis, Michael C.
, p. 22461 - 22468 (2021)
Heteroaromatic sulfinates are effective nucleophilic reagents in Pd0-catalyzed cross-coupling reactions with aryl halides. However, metal sulfinate salts can be challenging to purify, solubilize in reaction media, and are not tolerant to multi-step transformations. Here we introduce base-activated, latent sulfinate reagents: β-nitrile and β-ester sulfones. We show that under the cross-coupling conditions, these species generate the sulfinate salt in situ, which then undergo efficient palladium-catalyzed desulfinative cross-coupling with (hetero)aryl bromides to deliver a broad range of biaryls. These latent sulfinate reagents have proven to be stable through multi-step substrate elaboration, and amenable to scale-up.
Transition-Metal-Free Desulfinative Cross-Coupling of Heteroaryl Sulfinates with Grignard Reagents
Wei, Jun,Liang, Huamin,Ni, Chuanfa,Sheng, Rong,Hu, Jinbo
, (2019/02/05)
A mild cross-coupling reaction of heteroaryl sulfinates with Grignard reagents has been developed under transition-metal-free conditions. This study provides an example of the SO22- as a leaving group in an aromatic system and an effective methodology for the construction of C-C bond.
Pyridine sulfinates as general nucleophilic coupling partners in palladium-catalyzed cross-coupling reactions with aryl halides
Markovic, Tim,Rocke, Benjamin N.,Blakemore, David C.,Mascitti, Vincent,Willis, Michael C.
, p. 4437 - 4442 (2017/07/11)
Pyridine rings are ubiquitous in drug molecules; however, the pre-eminent reaction used to form carbon-carbon bonds in the pharmaceutical industry, the Suzuki-Miyaura cross-coupling reaction, often fails when applied to these structures. This phenomenon is most pronounced in 2-substituted pyridines, and results from the difficulty in preparing, the poor stability of, and low efficiency in reactions of pyridine-2-boronates. We demonstrate that by replacing these boronates with pyridine-2-sulfinates, a cross-coupling process of unrivalled scope and utility is realized. The corresponding 3-And 4-substituted pyridine variants are also efficient coupling partners. In addition, we apply these sulfinates in a library format to the preparation of medicinally relevant derivatives of the drugs varenicline (Chantix) and mepyramine (Anthisan).
Palladium-catalyzed C-H arylation using aryltrifluoroborates in conjunction with a MnIII oxidant under mild conditions
Seigerman, Cydney K.,Micyus, Tiffiny M.,Neufeldt, Sharon R.,Sanford, Melanie S.
, p. 5580 - 5587 (2013/06/27)
This paper describes the development of a mild Pd-catalyzed C-H arylation reaction using potassium aryltrifluoroborates in conjunction with Mn(OAc) 3 as the oxidant. The scope of this transformation is explored with a variety of different aryltrifluoroborates and arylpyridine substrates. Preliminary mechanistic studies suggest that the reaction proceeds via a high-valent Pd mechanism with C-H activation occurring at or before the rate determining step.
