Synthesis and asymmetric catalytic application of chiral imidazolium-phosphines derived from (1R,2R)-trans-diaminocyclohexane

R  Hodgson; R E  Douthwaite

doi:10.1016/j.jorganchem.2005.07.110

Synthesis and asymmetric catalytic application of chiral imidazolium-phosphines derived from (1R,2R)-trans-diaminocyclohexane

R Hodgson, R E Douthwaite

Chemistry

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

Abstract

Reaction between a chiral imidazole-amine precursor derived from (1R,2R)-trans-diaminocyclohexane and (PCl)-Cl-1 (where P-1 = PPh2, P(1,3,5-Me3C6H3)2, P(2,2'-O,O'-(1,1'-biphenyl), P((R)-(2,2'-O,O'-(1,1'-binaphthyl))) and P((S)-(2,2'-O,O'-(1,1'-binaphthyl)))) followed by RX (where R = Pr-n, Pr-i, CHPh2, X = Br; R = Pr-i, X = 1), respectively, gives a selection of chiral imidazolium-phosphine compounds. Deprotonation of the imidazolium Salt gives the corresponding NHC-P ligands that can be used in metal-mediated asymmetric catalytic applications. Catalytic reactions show that NHC-P ligands give a significantly greater rate of reaction for a palladium catalysed allylic substitution reaction in comparison to analogous di-NHC or NHC-imine ligands and that NHC-P hybrids are also effective for iridium catalysed transfer hydrogenation. (c) 2005 Elsevier B.V. All rights reserved.

Original language	English
Pages (from-to)	5822-5831
Number of pages	10
Journal	JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume	690
Issue number	24-25
DOIs	https://doi.org/10.1016/j.jorganchem.2005.07.110
Publication status	Published - 1 Dec 2005

Keywords

imidazolium salts
N-heterocyclic carbenes
catalysis
allylic substitution
transfer hydrogenation
N-HETEROCYCLIC CARBENES
TRANSFER HYDROGENATION
ALLYLIC ALKYLATION
IRIDIUM COMPLEXES
LIGANDS
PALLADIUM
ALKENES
RHODIUM
HYDROVINYLATION

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10.1016/j.jorganchem.2005.07.110

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@article{742b1f75a1ad4e1d989f795bb8c70e92,

title = "Synthesis and asymmetric catalytic application of chiral imidazolium-phosphines derived from (1R,2R)-trans-diaminocyclohexane",

abstract = "Reaction between a chiral imidazole-amine precursor derived from (1R,2R)-trans-diaminocyclohexane and (PCl)-Cl-1 (where P-1 = PPh2, P(1,3,5-Me3C6H3)2, P(2,2'-O,O'-(1,1'-biphenyl), P((R)-(2,2'-O,O'-(1,1'-binaphthyl))) and P((S)-(2,2'-O,O'-(1,1'-binaphthyl)))) followed by RX (where R = Pr-n, Pr-i, CHPh2, X = Br; R = Pr-i, X = 1), respectively, gives a selection of chiral imidazolium-phosphine compounds. Deprotonation of the imidazolium Salt gives the corresponding NHC-P ligands that can be used in metal-mediated asymmetric catalytic applications. Catalytic reactions show that NHC-P ligands give a significantly greater rate of reaction for a palladium catalysed allylic substitution reaction in comparison to analogous di-NHC or NHC-imine ligands and that NHC-P hybrids are also effective for iridium catalysed transfer hydrogenation. (c) 2005 Elsevier B.V. All rights reserved.",

keywords = "imidazolium salts, N-heterocyclic carbenes, catalysis, allylic substitution, transfer hydrogenation, N-HETEROCYCLIC CARBENES, TRANSFER HYDROGENATION, ALLYLIC ALKYLATION, IRIDIUM COMPLEXES, LIGANDS, PALLADIUM, ALKENES, RHODIUM, HYDROVINYLATION",

author = "R Hodgson and Douthwaite, {R E}",

year = "2005",

month = dec,

day = "1",

doi = "10.1016/j.jorganchem.2005.07.110",

language = "English",

volume = "690",

pages = "5822--5831",

journal = "JOURNAL OF ORGANOMETALLIC CHEMISTRY",

issn = "0022-328X",

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TY - JOUR

T1 - Synthesis and asymmetric catalytic application of chiral imidazolium-phosphines derived from (1R,2R)-trans-diaminocyclohexane

AU - Hodgson, R

AU - Douthwaite, R E

PY - 2005/12/1

Y1 - 2005/12/1

N2 - Reaction between a chiral imidazole-amine precursor derived from (1R,2R)-trans-diaminocyclohexane and (PCl)-Cl-1 (where P-1 = PPh2, P(1,3,5-Me3C6H3)2, P(2,2'-O,O'-(1,1'-biphenyl), P((R)-(2,2'-O,O'-(1,1'-binaphthyl))) and P((S)-(2,2'-O,O'-(1,1'-binaphthyl)))) followed by RX (where R = Pr-n, Pr-i, CHPh2, X = Br; R = Pr-i, X = 1), respectively, gives a selection of chiral imidazolium-phosphine compounds. Deprotonation of the imidazolium Salt gives the corresponding NHC-P ligands that can be used in metal-mediated asymmetric catalytic applications. Catalytic reactions show that NHC-P ligands give a significantly greater rate of reaction for a palladium catalysed allylic substitution reaction in comparison to analogous di-NHC or NHC-imine ligands and that NHC-P hybrids are also effective for iridium catalysed transfer hydrogenation. (c) 2005 Elsevier B.V. All rights reserved.

AB - Reaction between a chiral imidazole-amine precursor derived from (1R,2R)-trans-diaminocyclohexane and (PCl)-Cl-1 (where P-1 = PPh2, P(1,3,5-Me3C6H3)2, P(2,2'-O,O'-(1,1'-biphenyl), P((R)-(2,2'-O,O'-(1,1'-binaphthyl))) and P((S)-(2,2'-O,O'-(1,1'-binaphthyl)))) followed by RX (where R = Pr-n, Pr-i, CHPh2, X = Br; R = Pr-i, X = 1), respectively, gives a selection of chiral imidazolium-phosphine compounds. Deprotonation of the imidazolium Salt gives the corresponding NHC-P ligands that can be used in metal-mediated asymmetric catalytic applications. Catalytic reactions show that NHC-P ligands give a significantly greater rate of reaction for a palladium catalysed allylic substitution reaction in comparison to analogous di-NHC or NHC-imine ligands and that NHC-P hybrids are also effective for iridium catalysed transfer hydrogenation. (c) 2005 Elsevier B.V. All rights reserved.

KW - imidazolium salts

KW - N-heterocyclic carbenes

KW - catalysis

KW - allylic substitution

KW - transfer hydrogenation

KW - N-HETEROCYCLIC CARBENES

KW - TRANSFER HYDROGENATION

KW - ALLYLIC ALKYLATION

KW - IRIDIUM COMPLEXES

KW - LIGANDS

KW - PALLADIUM

KW - ALKENES

KW - RHODIUM

KW - HYDROVINYLATION

U2 - 10.1016/j.jorganchem.2005.07.110

DO - 10.1016/j.jorganchem.2005.07.110

M3 - Article

SN - 0022-328X

VL - 690

SP - 5822

EP - 5831

JO - JOURNAL OF ORGANOMETALLIC CHEMISTRY

JF - JOURNAL OF ORGANOMETALLIC CHEMISTRY

IS - 24-25

ER -