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. 2017 Feb 1;8(2):1015-1020.
doi: 10.1039/c6sc02587k. Epub 2016 Sep 23.

Heptamethylindenyl (Ind*) enables diastereoselective benzamidation of cyclopropenes via Rh(iii)-catalyzed C-H activation

Natthawat Semakul  1 , Kelvin E Jackson  2 , Robert S Paton  2 , Tomislav Rovis  1
Affiliations

Heptamethylindenyl (Ind*) enables diastereoselective benzamidation of cyclopropenes via Rh(iii)-catalyzed C-H activation

Natthawat Semakul et al. Chem Sci. .

Abstract

The diastereoselective coupling of O-substituted arylhydroxamates and cyclopropenes mediated by Rh(iii) catalysis was successfully developed. Through ligand development, the diastereoselectivity of this reaction was improved using a heptamethylindenyl (Ind*) ligand, which has been rationalized using quantum chemical calculations. In addition, the nature of the O-substituted ester of benzhydroxamic acid proved important for high diastereoselectivity. This transformation tolerates a variety of benzamides and cyclopropenes that furnish cyclopropa[c]dihydroisoquinolones with high diastereocontrol, which could then be easily transformed into synthetically useful building blocks for pharmaceuticals and bio-active molecules.

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Figures

Fig. 1
Fig. 1. (A) The use of cyclopropenes in Rh(iii) catalysis. (B) Examples of Cp ligands that improve selectivity. (C) This work.
Scheme 1
Scheme 1. Mechanistic experiments.
Scheme 2
Scheme 2. (A) Proposed reaction mechanism and (B) stereochemical model for diastereoselectivity. Gibbs energies in kcal mol–1.
Scheme 3
Scheme 3. Derivatizations of product.
See this image and copyright information in PMC

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