Rh^III‐Catalyzed C−H Activation of Aryl Hydroxamates for the Synthesis of Isoindolinones

Abstract

RhIII‐catalyzed C−H functionalization reaction yielding isoindolinones from aryl hydroxamates and ortho‐substituted styrenes is reported. The reaction proceeds smoothly under mild conditions at room temperature, and tolerates a range of functional groups. Experimental and computational investigations support that the high regioselectivity observed for these substrates results from the presence of an ortho‐substituent embedded in the styrene. The resulting isoindolinones are valuable building blocks for the synthesis of bioactive compounds. They provide easy access to the natural‐product‐like compounds, isoindolobenzazepines, in a one‐pot two‐step reaction. Selected isoindolinones inhibited Hedgehog (Hh)‐dependent differentiation of multipotent murine mesenchymal progenitor stem cells into osteoblasts.

Applications of Chiral Cyclopentadienyl (Cpx) Metal Complexes in Asymmetric Catalysis

“…This reaction is of high importance as it proves that the formation of the five-membered ring 34 is caused by the use of OBoc-protected hydroxamates 32. [35] This finding disproves the previous assignment of these adducts as being six-membered ring dihydroisoquinolone regioisomers. [36] The asymmetric synthesis of oxindolinones was accomplished by Wang et al in 2018, using α,α,di-fluoro-alkyne derivatives 35.…”

Corrigendum: Rhodium(III) Complex with a Bulky Cyclopentadienyl Ligand as a Catalyst for Regioselective Synthesis of Dihydroisoquinolones through C−H Activation of Arylhydroxamic Acids

“…and H. Waldmann et al. have independently discovered that 4 p has in fact the structure of 3‐benzylisoindolin‐1‐one (this was confirmed by X‐ray structures of chloro‐substituted derivatives) [2, 3] . Therefore, we provide the corrected Schemes 5 and 6 and the corresponding text for our article as shown below.…”

Dual Role of the Rhodium(III) Catalyst in C–H Activation: [4 + 3] Annulation of Amide with Allylic Alcohols to 7-Membered Lactams

“…Along with this, the synthesis of five-membered and six-membered heterocyclic rings has been reported by several groups using directed C–H activation followed by annulation reaction of secondary benzamide derivatives using various transition metal catalysts. However, the synthesis of 5- and 6-membered heterocycles is simple and common.…”