39729-00-5Relevant articles and documents
Overcoming Scope Limitations in Cross-Coupling of Diazo Nucleophiles by Manipulating Catalyst Speciation and Using Flow Diazo Generation
Sullivan, Ryan J.,Freure, Garrett P.R.,Newman, Stephen G.
, p. 5623 - 5630 (2019/06/05)
The accessible scope of palladium-catalyzed diazo cross-coupling reactions has been expanded to include aryl chlorides by controlled diazo slow addition. The success of this strategy is based on manipulating speciation within the catalytic cycle through starvation of the diazo reagent to make the Pd(II) oxidative intermediate the resting state. The strategy is also applicable to cross-coupling reactions with aryl bromides and, in combination with safe, on-demand flow generation of nonstabilized diazo reagents, has been used to greatly expand the scope of applicable diazo compounds for this chemistry as well. Lastly, DFT calculations have provided insight into the mechanism and support for the proposed explanation for success of the slow addition strategy.
Ruthenium-Catalyzed C-H Allylation of Alkenes with Allyl Alcohols via C-H Bond Activation in Aqueous Solution
Wu, Xiaowei,Ji, Haitao
supporting information, p. 12094 - 12102 (2018/10/02)
A robust Ru(II)-catalyzed C-H allylation of electron-deficient alkenes with allyl alcohols in aqueous solution is reported. This method provides a straightforward and efficient access to the synthetically useful 1,4-diene skeletons. With the assistance of the N-methoxycarbamoyl directing group, this allylation reaction features a broad substrate scope with good functional group tolerance, excellent regio- and stereoselectivity, absence of metal oxidants, water-tolerant solvents, and mild reaction conditions. The mechanistic studies indicate that the process of the reversible C-H bond ruthenation is assisted by acetate, and the rate-determining step is unlikely to be the step of C-H bond cleavage.
Switchable C-H Functionalization of N-Tosyl Acrylamides with Acryloylsilanes
Song, Shengjin,Lu, Ping,Liu, Huan,Cai, Sai-Hu,Feng, Chao,Loh, Teck-Peng
, p. 2869 - 2872 (2017/06/13)
A controllable Rh-catalyzed protocol to access alkylation and alkenylation-annulation of N-tosyl acrylamide with acryloyl silane is reported. In contrast to the directing group or catalyst-dependent divergent sp2 C-H alkylation/alkenylation, the intrinsic property of acryloylsilane allows the switchable reaction manifold, thereby affording either alkylation or annulation products with slight modification of the reaction conditions.
