Neighboring group participation of the indole nucleus: An unusual DAST-mediated rearrangerment reaction

D.J. Hallett; U. Gerhard; S.C. Goodacre; L. Hitzel; T.J. Sparey; S. Thomas; M. Rowley; R.G. Ball

doi:10.1021/jo0004759

Neighboring group participation of the indole nucleus: An unusual DAST-mediated rearrangerment reaction

D.J. Hallett, U. Gerhard, S.C. Goodacre, L. Hitzel, T.J. Sparey, S. Thomas, M. Rowley, R.G. Ball

Research output: Contribution to journal › Article › peer-review

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Abstract

A rearrangement reaction involving the indole nucleus was investigated using stereochemical markers and low-temperature NMR experiments. Treatment of(3S,4S)-3-hydroxy-4-(2-phenyl-1H-indol-3-yl)-piperidine-1-carboxylic acid benzyl ester (> 90% ee) with diethylaminosulfur trifluoride gave stereospecifically (3S,4S)-4-fluoro-3-(2-phenyl-1H-indol-3-yl)-piperidine-1-carboxylic acid benzyl ester (> 90% ee) with complete regioselectivity. The initial formation of a reactive spirocyclopropyl-3H-indole intermediate is believed to be responsible for the stereo- and regiochemical outcome of the reaction.

Original language	English
Pages (from-to)	4984-4993
Number of pages	10
Journal	Journal of Organic Chemistry
Volume	65
Issue number	16
DOIs	https://doi.org/10.1021/jo0004759
Publication status	Published - 11 Aug 2000

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abstract = "A rearrangement reaction involving the indole nucleus was investigated using stereochemical markers and low-temperature NMR experiments. Treatment of(3S,4S)-3-hydroxy-4-(2-phenyl-1H-indol-3-yl)-piperidine-1-carboxylic acid benzyl ester (> 90% ee) with diethylaminosulfur trifluoride gave stereospecifically (3S,4S)-4-fluoro-3-(2-phenyl-1H-indol-3-yl)-piperidine-1-carboxylic acid benzyl ester (> 90% ee) with complete regioselectivity. The initial formation of a reactive spirocyclopropyl-3H-indole intermediate is believed to be responsible for the stereo- and regiochemical outcome of the reaction.",

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T2 - An unusual DAST-mediated rearrangerment reaction

AU - Hallett, D.J.

AU - Gerhard, U.

AU - Goodacre, S.C.

AU - Hitzel, L.

AU - Sparey, T.J.

AU - Thomas, S.

AU - Rowley, M.

AU - Ball, R.G.

PY - 2000/8/11

Y1 - 2000/8/11

N2 - A rearrangement reaction involving the indole nucleus was investigated using stereochemical markers and low-temperature NMR experiments. Treatment of(3S,4S)-3-hydroxy-4-(2-phenyl-1H-indol-3-yl)-piperidine-1-carboxylic acid benzyl ester (> 90% ee) with diethylaminosulfur trifluoride gave stereospecifically (3S,4S)-4-fluoro-3-(2-phenyl-1H-indol-3-yl)-piperidine-1-carboxylic acid benzyl ester (> 90% ee) with complete regioselectivity. The initial formation of a reactive spirocyclopropyl-3H-indole intermediate is believed to be responsible for the stereo- and regiochemical outcome of the reaction.

AB - A rearrangement reaction involving the indole nucleus was investigated using stereochemical markers and low-temperature NMR experiments. Treatment of(3S,4S)-3-hydroxy-4-(2-phenyl-1H-indol-3-yl)-piperidine-1-carboxylic acid benzyl ester (> 90% ee) with diethylaminosulfur trifluoride gave stereospecifically (3S,4S)-4-fluoro-3-(2-phenyl-1H-indol-3-yl)-piperidine-1-carboxylic acid benzyl ester (> 90% ee) with complete regioselectivity. The initial formation of a reactive spirocyclopropyl-3H-indole intermediate is believed to be responsible for the stereo- and regiochemical outcome of the reaction.

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Neighboring group participation of the indole nucleus: An unusual DAST-mediated rearrangerment reaction

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