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. 2016 Sep 1;7(9):5934-5938.
doi: 10.1039/c6sc01075j. Epub 2016 May 24.

Rhodium catalyzed diastereoselective synthesis of 2,2,3,3-tetrasubstituted indolines from N-sulfonyl-1,2,3-triazoles and ortho-vinylanilines

Dongari Yadagiri  1 , Angula Chandra Shekar Reddy  1 , Pazhamalai Anbarasan  1
Affiliations

Rhodium catalyzed diastereoselective synthesis of 2,2,3,3-tetrasubstituted indolines from N-sulfonyl-1,2,3-triazoles and ortho-vinylanilines

Dongari Yadagiri et al. Chem Sci. .

Abstract

An efficient diastereoselective rhodium catalyzed synthesis of indolines possessing two contiguous tetrasubstituted carbon centers has been achieved with good to excellent yields using ortho-vinylanilines and iminocarbenes derived from N-sulfonyl-1,2,3-triazoles. The reaction affords excellent cis-diastereoselectivity through the initial formation of a N-ylide followed by intramolecular trapping with unactivated alkenes via an ene-type reaction with a well-organized transition state, namely intramolecular carbenylative amination of alkenes. The developed transformation was further extended to the successful synthesis of tricyclic compounds, imidazoindolines, through reduction and hypervalent iodine mediated oxidative cyclization.

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Figures

Fig. 1
Fig. 1. Representative examples of indoline alkaloids.
Scheme 1
Scheme 1. Rhodium-catalyzed reactions of N-sulfonyl-1,2,3-triazoles.
Scheme 2
Scheme 2. Rhodium catalyzed carbenylative amination: scope of the triazoles 1. R1 = p-methylbenzyl.
Scheme 3
Scheme 3. Rhodium catalyzed carbenylative amination: scope of the o-vinylanilines 2. †NMR yield.
Scheme 4
Scheme 4. (a) Plausible mechanism; (b) proposed transition state for the ene-type reaction.
Scheme 5
Scheme 5. Synthesis of imidazoindoline 6a.
Scheme 6
Scheme 6. Synthesis of imidazoindolines 6. †1H NMR yield.
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