Rhodium(iii)-catalyzed oxidative alkylation of N-aryl-7-azaindoles with cyclopropanols

Abstract

An efficient Rh(iii)-catalyzed C–H oxidative alkylation of N-aryl-7-azaindoles with cyclopropanols by merging tandem C–H and C–C cleavage was developed.

Ring‐Opening Cross‐Coupling/Cyclization Reaction of Cyclopropanols with Organic Compounds

“…Abstraction of an H-atom from cycloalkanol by sulfate anion radical A generated the oxygen-centered radical B that underwent the CÀ C bond cleavage to provide alkyl radical C. Reaction between radical intermediate C and cyclic aldimine 18, give radical D. Then, deprotonation of intermediate D by sulfate anion and simultaneously conversion of Ag(II) to Ag(I) through a SET process, delivered to target product 19. Another method in CÀ H functionalization of heterocycle compounds is mediated by rhodium(III) as the catalyst described by Liu et al [19] In their work, CÀ H and CÀ C bonds cleavage furnished to β-aryl ketone derivatives through the reaction N-aryl-7-azaindoles with cyclopropanols. Conversion of coupling products to 7-azaindolecontaining π-extended polycyclic heteroarenes utilizing Cu-(OAc) 2 was also performed in this work.…”

Rh(iii)-catalyzed [4 + 1] cyclization of aryl substituted pyrazoles with cyclopropanols via C–H activation

“…Cyclopropanols have been widely employed in synthetic chemistry in recent years due to their easy availability and unique reactivity. 7,8 In 2017, Li's group developed Rh( iii )-catalyzed C–H activation of imidamides with cyclopropanols to obtain 2-substituted quinolines (Scheme 1a). 9 In 2021, Yu's group reported cobalt-catalyzed C–H/N–H functionalization and [4 + 1] annulation of N -(quinolin-8-yl)benzamide and cyclopropanols to afford isoindolin-1-ones (Scheme 1b).…”

How Strain-Release Determines Chemoselectivity: A Mechanistic Study of Rhodium-Catalyzed Bicyclo[1.1.0]butane Activation

“…Strained carbocycles have garnered significant research attention in organic synthesis because such skeletons exist widely in pharmaceuticals, natural products, and biologically active molecules. − Furthermore, they can be easily transformed to target functional groups through simple coupling protocols. − Among such compounds, bicyclo[1.1.0]­butanes (BCBs) have received extensive attention because they exhibit π-bond-type behavior owing to their pronounced bond-angle distortions, endowing them with high reactivity. − BCB derivatives exhibit versatile reactivity, and in recent decades, they have been widely employed in the synthesis of multifunctional molecules containing bicyclo[1.1.1]­pentane, − cyclopropane, − cyclobutane, , and azetidine moieties, − which serve as bioisosteres in the development and modification of pharmaceuticals.…”