Catalytic electronic activation as a tool for the addition of stabilised nucleophiles to allylic alcohols

P J Black; M G Edwards; J M J Williams

doi:10.1016/j.tet.2004.10.009

Catalytic electronic activation as a tool for the addition of stabilised nucleophiles to allylic alcohols

P J Black, M G Edwards, J M J Williams

Department of Chemistry

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21 Citations (SciVal)

Abstract

This paper describes the activation of 2-cyclohexen-1-ol (1) and 2-cyclopenten-1-ol (11) through the use of aluminium-catalysed transfer hydrogenation. The electronically activated substrates are demonstrated to undergo facile conjugate addition and, when the alcohol functional group is subsequently restored in a one-pot procedure, this leads to an indirect addition of nucleophiles to allylic alcohols. This novel methodology has been termed catalytic electronic activation. The aluminium tert-butoxide catalysed conversion of 2-cyclohexen-1-ol (1) into 2-(3-hydroxycyclohexyl)-2-methylmalononitrile (18) and 2-cyclopenten-1-ol (11) into 2-(3-hydroxycyclopentyl)-2-methylmalononitrile (16) in 90 and 60% yield, respectively has been demonstrated through an efficient domino Oppenauer/Michael addition/Meerwein-Ponndorf-Verley process. (C) 2004 Elsevier Ltd. All rights reserved.

Original language	English
Pages (from-to)	1363-1374
Number of pages	12
Journal	Tetrahedron
Volume	61
Issue number	5
DOIs	https://doi.org/10.1016/j.tet.2004.10.009
Publication status	Published - 2005

Bibliographical note

ID number: ISI:000226565400034

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10.1016/j.tet.2004.10.009

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title = "Catalytic electronic activation as a tool for the addition of stabilised nucleophiles to allylic alcohols",

abstract = "This paper describes the activation of 2-cyclohexen-1-ol (1) and 2-cyclopenten-1-ol (11) through the use of aluminium-catalysed transfer hydrogenation. The electronically activated substrates are demonstrated to undergo facile conjugate addition and, when the alcohol functional group is subsequently restored in a one-pot procedure, this leads to an indirect addition of nucleophiles to allylic alcohols. This novel methodology has been termed catalytic electronic activation. The aluminium tert-butoxide catalysed conversion of 2-cyclohexen-1-ol (1) into 2-(3-hydroxycyclohexyl)-2-methylmalononitrile (18) and 2-cyclopenten-1-ol (11) into 2-(3-hydroxycyclopentyl)-2-methylmalononitrile (16) in 90 and 60% yield, respectively has been demonstrated through an efficient domino Oppenauer/Michael addition/Meerwein-Ponndorf-Verley process. (C) 2004 Elsevier Ltd. All rights reserved.",

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T1 - Catalytic electronic activation as a tool for the addition of stabilised nucleophiles to allylic alcohols

AU - Black, P J

AU - Edwards, M G

AU - Williams, J M J

N1 - ID number: ISI:000226565400034

PY - 2005

Y1 - 2005

N2 - This paper describes the activation of 2-cyclohexen-1-ol (1) and 2-cyclopenten-1-ol (11) through the use of aluminium-catalysed transfer hydrogenation. The electronically activated substrates are demonstrated to undergo facile conjugate addition and, when the alcohol functional group is subsequently restored in a one-pot procedure, this leads to an indirect addition of nucleophiles to allylic alcohols. This novel methodology has been termed catalytic electronic activation. The aluminium tert-butoxide catalysed conversion of 2-cyclohexen-1-ol (1) into 2-(3-hydroxycyclohexyl)-2-methylmalononitrile (18) and 2-cyclopenten-1-ol (11) into 2-(3-hydroxycyclopentyl)-2-methylmalononitrile (16) in 90 and 60% yield, respectively has been demonstrated through an efficient domino Oppenauer/Michael addition/Meerwein-Ponndorf-Verley process. (C) 2004 Elsevier Ltd. All rights reserved.

AB - This paper describes the activation of 2-cyclohexen-1-ol (1) and 2-cyclopenten-1-ol (11) through the use of aluminium-catalysed transfer hydrogenation. The electronically activated substrates are demonstrated to undergo facile conjugate addition and, when the alcohol functional group is subsequently restored in a one-pot procedure, this leads to an indirect addition of nucleophiles to allylic alcohols. This novel methodology has been termed catalytic electronic activation. The aluminium tert-butoxide catalysed conversion of 2-cyclohexen-1-ol (1) into 2-(3-hydroxycyclohexyl)-2-methylmalononitrile (18) and 2-cyclopenten-1-ol (11) into 2-(3-hydroxycyclopentyl)-2-methylmalononitrile (16) in 90 and 60% yield, respectively has been demonstrated through an efficient domino Oppenauer/Michael addition/Meerwein-Ponndorf-Verley process. (C) 2004 Elsevier Ltd. All rights reserved.

U2 - 10.1016/j.tet.2004.10.009

DO - 10.1016/j.tet.2004.10.009

M3 - Article

SN - 0040-4020

VL - 61

SP - 1363

EP - 1374

JO - Tetrahedron

JF - Tetrahedron

IS - 5

ER -

Catalytic electronic activation as a tool for the addition of stabilised nucleophiles to allylic alcohols

Abstract

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