Platinum-Catalysed Ring-Opening Isomerisation of Piperidine Cyclopropanes

Viktor Barát; Sivarajan Kasinathan; Roderick W. Bates

doi:10.1002/ajoc.201700706

Platinum-Catalysed Ring-Opening Isomerisation of Piperidine Cyclopropanes

Viktor Barát, Sivarajan Kasinathan, Roderick W. Bates^*

^*Corresponding author for this work

Nanyang Technological University

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

1 Citation (Scopus)

Abstract

A range of cyclopropyl-fused N-tosyl piperidines have been synthesised and shown to undergo ring-opening isomerisation on treatment with platinum(II) catalysts. The products can have either an endo-cyclic or exo-cyclic double bond. The selectivity is influenced by reaction temperature, solvent and, most significantly, the catalyst. A mechanism involving C−C bond activation and β-hydride elimination is proposed. When β-hydride elimination is blocked, a stereospecific platinum-driven Wagner–Meerwein shift is observed.

Original language	English
Pages (from-to)	815-818
Number of pages	4
Journal	Asian Journal of Organic Chemistry
Volume	7
Issue number	4
DOIs	https://doi.org/10.1002/ajoc.201700706
Publication status	Published - Apr 2018
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ASJC Scopus Subject Areas

Organic Chemistry

Keywords

cyclopropane
isomerisation
platinum
ring-opening
Wagner–Meerwein reaction

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10.1002/ajoc.201700706

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title = "Platinum-Catalysed Ring-Opening Isomerisation of Piperidine Cyclopropanes",

abstract = "A range of cyclopropyl-fused N-tosyl piperidines have been synthesised and shown to undergo ring-opening isomerisation on treatment with platinum(II) catalysts. The products can have either an endo-cyclic or exo-cyclic double bond. The selectivity is influenced by reaction temperature, solvent and, most significantly, the catalyst. A mechanism involving C−C bond activation and β-hydride elimination is proposed. When β-hydride elimination is blocked, a stereospecific platinum-driven Wagner–Meerwein shift is observed.",

keywords = "cyclopropane, isomerisation, platinum, ring-opening, Wagner–Meerwein reaction",

author = "Viktor Bar{\'a}t and Sivarajan Kasinathan and Bates, {Roderick W.}",

note = "Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2018",

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doi = "10.1002/ajoc.201700706",

language = "English",

volume = "7",

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TY - JOUR

T1 - Platinum-Catalysed Ring-Opening Isomerisation of Piperidine Cyclopropanes

AU - Barát, Viktor

AU - Kasinathan, Sivarajan

AU - Bates, Roderick W.

PY - 2018/4

Y1 - 2018/4

N2 - A range of cyclopropyl-fused N-tosyl piperidines have been synthesised and shown to undergo ring-opening isomerisation on treatment with platinum(II) catalysts. The products can have either an endo-cyclic or exo-cyclic double bond. The selectivity is influenced by reaction temperature, solvent and, most significantly, the catalyst. A mechanism involving C−C bond activation and β-hydride elimination is proposed. When β-hydride elimination is blocked, a stereospecific platinum-driven Wagner–Meerwein shift is observed.

AB - A range of cyclopropyl-fused N-tosyl piperidines have been synthesised and shown to undergo ring-opening isomerisation on treatment with platinum(II) catalysts. The products can have either an endo-cyclic or exo-cyclic double bond. The selectivity is influenced by reaction temperature, solvent and, most significantly, the catalyst. A mechanism involving C−C bond activation and β-hydride elimination is proposed. When β-hydride elimination is blocked, a stereospecific platinum-driven Wagner–Meerwein shift is observed.

KW - cyclopropane

KW - isomerisation

KW - platinum

KW - ring-opening

KW - Wagner–Meerwein reaction

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DO - 10.1002/ajoc.201700706

M3 - Article

AN - SCOPUS:85045532103

SN - 2193-5807

VL - 7

SP - 815

EP - 818

JO - Asian Journal of Organic Chemistry

JF - Asian Journal of Organic Chemistry

IS - 4

ER -

Platinum-Catalysed Ring-Opening Isomerisation of Piperidine Cyclopropanes

Abstract

Bibliographical note

ASJC Scopus Subject Areas

Keywords

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