Rhodium(iii)-catalyzed chemodivergent annulations between N-methoxybenzamides and sulfoxonium ylides via C–H activation

Abstract

Chemodivergent and redox-neutral annulations between N-methoxybenzamides and sulfoxonium ylides have been realized via Rh(iii)-catalyzed C-H activation. The sulfoxonium ylide acts as a carbene precursor, and coupling occurs under acid-controlled conditions, where Zn(OTf) and PivOH promote chemodivergent cyclizations.

Rhodium(III)-Catalyzed [4+2] Annulation via C-H Activation: Synthesis of Multi-Substituted Naphthalenone Sulfoxonium Ylides

“…Recently, sulfoxonium ylides have been identified as a precursor of carbenoid in the transition-metal-catalyzed reactions [30,31,32]. Being successfully applied to the multi-kilogram synthesis of drug intermediates via Ir(I)-catalyzed reactions in industry [33,34] sulfoxonium ylides have also been widely investigated in the Rh(III)- [35,36,37,38,39,40,41,42,43,44], Co(III)- [45], or Ru(II)-catalyzed [46,47] C-H bond functionalization. However, the application of sulfoxonium ylides is severely limited by its substrate scope because the C1 position substitution in the ylide center is only H. To overcome such limitations, Bayer and co-workers reported the synthesis of bis-substituted sulfoxonium ylides via rhodium-catalyzed coupling of iodonium ylides with sulfoxides (Scheme 1b) [48].…”

Cp*IrIII‐Catalyzed [3+2] Annulations of N‐Aryl‐2‐aminopyrimidines with Sulfoxonium Ylides to Access 2‐Alkyl Indoles Through C–H Bond Activation

“…In 2017, Li and co‐workers reported sulfoxonium ylide as carbene precursor in Rh III ‐Catalyzed C–H acylmethylation of arene . Subsequently, using sulfoxonium ylides as C2 or C1 synthon with homogeneous rhodium, iridium or ruthenium as the catalysts, a number of condensed heterocycles such as isoquinolones, isocoumarins, naphthols, indazoles and indoles were achieved via ortho C–H activation/annulation. Yet, to the best of our knowledge, the use of sulfoxonium ylides for the synthesis of 2‐alkyl indoles remains is underdeveloped and Cp * Ir III catalysts have not been used.…”

Ruthenium(II)-Catalyzed Homocoupling of α-Carbonyl Sulfoxonium Ylides Under Mild Conditions: Methodology Development and Mechanistic DFT Study

“…It was generally proposed that the cyclic product was formed by the first generation of an acylmethylation intermediate in similar cascade reactions. (Chen et al, 2018;Hu et al, 2018aHu et al, ,b, 2019Liang et al, 2018;Shi et al, 2018;Xiao et al, 2018;Xie et al, 2018bXie et al, , 2019Xie H. et al, 2018;Xu et al, 2018;Zhou et al, 2018;Cai et al, 2019;Chen P. et al, 2019;Cui et al, 2019;Huang et al, 2019;Lai et al, 2019;Liu et al, 2019;Luo et al, 2019;Lv et al, 2019;Nie et al, 2019;Shen et al, 2019;Wu C. et al, 2019;Zhang et al, 2019Zhang et al, , 2020Wu et al, 2020). Further transformations from IM6 were explored theoretically to confirm whether the acylmethylation intermediate (IM8) is key in the formation of 2a (Figure 2).…”

“…2012; Gao et al, 2015;Zhou et al, 2015;Chen et al, 2016;Wang et al, 2017Wang et al, , 2018Pan et al, 2018;Xie et al, 2018a;Xie H. et al, 2018), in the current report we present a combined experimental and theoretical study of ruthenium(II)-catalyzed homocoupling of α-carbonyl sulfoxonium ylides, affording a variety of isocoumarin derivatives under mild conditions (Scheme 1C). (Liang et al, 2018;Xu et al, 2018;Huang et al, 2019;Zhou et al, 2019;Wen et al, 2020;Zhu et al, 2020). DFT calculations (Shan et al, 2016(Shan et al, , 2018Yu et al, 2017;Lian et al, 2019;Ling et al, 2019) suggested that the reaction is realized by a formal [3+3] annulation initiated by Ru(II)-catalyzed C-H activation.…”