On the synthesis of α-amino sulfoxides

Peter J. Rayner; Giacomo Gelardi; Peter O'Brien; Richard A J Horan; David C. Blakemore

doi:10.1039/c4ob00567h

On the synthesis of α-amino sulfoxides

Peter J. Rayner, Giacomo Gelardi, Peter O'Brien^*, Richard A J Horan, David C. Blakemore

^*Corresponding author for this work

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

Abstract

A synthetic study on the preparation of N-Boc α-amino sulfoxides has revealed an unexpected instability which is believed to be due to α-elimination of the sulfoxide to give an iminium ion. Full synthetic details are reported on two main synthetic routes: lithiation and sulfinate trapping of N-Boc heterocycles and oxidation of N-Boc α-amino sulfides. Six novel α-amino sulfoxides were successfully prepared and isolated. It is speculated that four other α-amino sulfoxides were synthesised but could not be isolated due to their propensity to α-eliminate the sulfoxide. Ultimately, a stable, cyclic N-Boc α-amino sulfoxide was prepared and this successful synthesis relied on the α-amino sulfoxide being part of a bicyclic [3.1.0] fused ring system that could not undergo α-elimination of the sulfoxide.

Original language	English
Pages (from-to)	3499-3512
Number of pages	14
Journal	Organic and Biomolecular Chemistry
Volume	12
Issue number	21
DOIs	https://doi.org/10.1039/c4ob00567h
Publication status	Published - 7 Jun 2014

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title = "On the synthesis of α-amino sulfoxides",

abstract = "A synthetic study on the preparation of N-Boc α-amino sulfoxides has revealed an unexpected instability which is believed to be due to α-elimination of the sulfoxide to give an iminium ion. Full synthetic details are reported on two main synthetic routes: lithiation and sulfinate trapping of N-Boc heterocycles and oxidation of N-Boc α-amino sulfides. Six novel α-amino sulfoxides were successfully prepared and isolated. It is speculated that four other α-amino sulfoxides were synthesised but could not be isolated due to their propensity to α-eliminate the sulfoxide. Ultimately, a stable, cyclic N-Boc α-amino sulfoxide was prepared and this successful synthesis relied on the α-amino sulfoxide being part of a bicyclic [3.1.0] fused ring system that could not undergo α-elimination of the sulfoxide.",

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AU - Rayner, Peter J.

AU - Gelardi, Giacomo

AU - O'Brien, Peter

AU - Horan, Richard A J

AU - Blakemore, David C.

PY - 2014/6/7

Y1 - 2014/6/7

N2 - A synthetic study on the preparation of N-Boc α-amino sulfoxides has revealed an unexpected instability which is believed to be due to α-elimination of the sulfoxide to give an iminium ion. Full synthetic details are reported on two main synthetic routes: lithiation and sulfinate trapping of N-Boc heterocycles and oxidation of N-Boc α-amino sulfides. Six novel α-amino sulfoxides were successfully prepared and isolated. It is speculated that four other α-amino sulfoxides were synthesised but could not be isolated due to their propensity to α-eliminate the sulfoxide. Ultimately, a stable, cyclic N-Boc α-amino sulfoxide was prepared and this successful synthesis relied on the α-amino sulfoxide being part of a bicyclic [3.1.0] fused ring system that could not undergo α-elimination of the sulfoxide.

AB - A synthetic study on the preparation of N-Boc α-amino sulfoxides has revealed an unexpected instability which is believed to be due to α-elimination of the sulfoxide to give an iminium ion. Full synthetic details are reported on two main synthetic routes: lithiation and sulfinate trapping of N-Boc heterocycles and oxidation of N-Boc α-amino sulfides. Six novel α-amino sulfoxides were successfully prepared and isolated. It is speculated that four other α-amino sulfoxides were synthesised but could not be isolated due to their propensity to α-eliminate the sulfoxide. Ultimately, a stable, cyclic N-Boc α-amino sulfoxide was prepared and this successful synthesis relied on the α-amino sulfoxide being part of a bicyclic [3.1.0] fused ring system that could not undergo α-elimination of the sulfoxide.

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JO - Organic and Biomolecular Chemistry

JF - Organic and Biomolecular Chemistry

IS - 21

ER -

On the synthesis of α-amino sulfoxides

Abstract

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