Rhodium catalysts derived from a fluorinated phanephos ligand are highly active catalysts for direct asymmetric reductive amination of secondary amines

Sophie H. Gilbert; Sergey Tin; José A. Fuentes; Tamara Fanjul; Matthew L. Clarke

doi:10.1016/j.tet.2020.131863

Rhodium catalysts derived from a fluorinated phanephos ligand are highly active catalysts for direct asymmetric reductive amination of secondary amines

Sophie H. Gilbert, Sergey Tin, José A. Fuentes, Tamara Fanjul, Matthew L. Clarke^*

^*Corresponding author for this work

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

Abstract

An asymmetric hydrogenation of enamines is efficiently catalysed by rhodium complexed with a fluorinated version of the planar chiral paracyclophane-diphosphine ligand, Phanephos. This catalyst was shown to be very active, with examples operating at just 0.1 mol% of catalyst. This catalyst was then successfully adapted to Direct Asymmetric Reductive Amination, leading to the formation of several tertiary amines with moderate e.e., if activated ketone/amine partners are used.

Original language	English
Article number	131863
Journal	Tetrahedron
Volume	In Press
Early online date	10 Dec 2020
DOIs	https://doi.org/10.1016/j.tet.2020.131863
Publication status	E-pub ahead of print - 10 Dec 2020

Keywords

Enamine hydrogenation
Electronic effects
Enantioselective hydrogenation
Planar chirality
Deuterium labelling

Access to Document

10.1016/j.tet.2020.131863

Gilbert_2020_Tetrahedron_Rhodium-catalysts_AAM
Copyright © 2020 Elsevier Ltd. All rights reserved. This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1016/j.tet.2020.131863
Accepted author manuscript, 745 KBLicence: CC BY-NC-ND

Cite this

@article{00adc5db81954b51a13bbaae19ade6b5,

title = "Rhodium catalysts derived from a fluorinated phanephos ligand are highly active catalysts for direct asymmetric reductive amination of secondary amines",

abstract = "An asymmetric hydrogenation of enamines is efficiently catalysed by rhodium complexed with a fluorinated version of the planar chiral paracyclophane-diphosphine ligand, Phanephos. This catalyst was shown to be very active, with examples operating at just 0.1 mol% of catalyst. This catalyst was then successfully adapted to Direct Asymmetric Reductive Amination, leading to the formation of several tertiary amines with moderate e.e., if activated ketone/amine partners are used.",

keywords = "Enamine hydrogenation, Electronic effects, Enantioselective hydrogenation, Planar chirality, Deuterium labelling",

author = "Gilbert, {Sophie H.} and Sergey Tin and Fuentes, {Jos{\'e} A.} and Tamara Fanjul and Clarke, {Matthew L.}",

note = "We would like to thank the University of St Andrews, and the EPSRC Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT) for financial support [Ph.D. studentship to SHG (PhD 2019); Grant code: EP/L016419/1], and Dr Reddys (EU Ltd.) for co-supporting a University studentship to ST (PhD 2017).",

year = "2020",

month = dec,

day = "10",

doi = "10.1016/j.tet.2020.131863",

language = "English",

volume = "In Press",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier",

}

TY - JOUR

T1 - Rhodium catalysts derived from a fluorinated phanephos ligand are highly active catalysts for direct asymmetric reductive amination of secondary amines

AU - Gilbert, Sophie H.

AU - Tin, Sergey

AU - Fuentes, José A.

AU - Fanjul, Tamara

AU - Clarke, Matthew L.

N1 - We would like to thank the University of St Andrews, and the EPSRC Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT) for financial support [Ph.D. studentship to SHG (PhD 2019); Grant code: EP/L016419/1], and Dr Reddys (EU Ltd.) for co-supporting a University studentship to ST (PhD 2017).

PY - 2020/12/10

Y1 - 2020/12/10

N2 - An asymmetric hydrogenation of enamines is efficiently catalysed by rhodium complexed with a fluorinated version of the planar chiral paracyclophane-diphosphine ligand, Phanephos. This catalyst was shown to be very active, with examples operating at just 0.1 mol% of catalyst. This catalyst was then successfully adapted to Direct Asymmetric Reductive Amination, leading to the formation of several tertiary amines with moderate e.e., if activated ketone/amine partners are used.

AB - An asymmetric hydrogenation of enamines is efficiently catalysed by rhodium complexed with a fluorinated version of the planar chiral paracyclophane-diphosphine ligand, Phanephos. This catalyst was shown to be very active, with examples operating at just 0.1 mol% of catalyst. This catalyst was then successfully adapted to Direct Asymmetric Reductive Amination, leading to the formation of several tertiary amines with moderate e.e., if activated ketone/amine partners are used.

KW - Enamine hydrogenation

KW - Electronic effects

KW - Enantioselective hydrogenation

KW - Planar chirality

KW - Deuterium labelling

UR - https://www.sciencedirect.com/science/article/pii/S0040402020311212?via=ihub#appsec1

U2 - 10.1016/j.tet.2020.131863

DO - 10.1016/j.tet.2020.131863

M3 - Article

SN - 0040-4020

VL - In Press

JO - Tetrahedron

JF - Tetrahedron

M1 - 131863

ER -

Rhodium catalysts derived from a fluorinated phanephos ligand are highly active catalysts for direct asymmetric reductive amination of secondary amines

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

CRITICAT CDT: Critical Resource Catalysis - CRITICAT