CO-free enantioselective hydroformylation of functionalised alkenes: using a dual catalyst system to give improved selectivity and yield

Rachael Pittaway; Paul Dingwall; José Fuentes; Matt Clarke

doi:10.1002/adsc.201900640

CO-free enantioselective hydroformylation of functionalised alkenes: using a dual catalyst system to give improved selectivity and yield

Rachael Pittaway, Paul Dingwall, José Fuentes, Matt Clarke

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

Abstract

The scope of carbon monoxide-free Asymmetric Transfer HydroFormylation (ATHF) procedures using a highly active single catalyst system derived from 1,2-bis-((2,5)-diphenylphospholano)ethane as chiral ligand has been studied. This reveals some highly successful reactions, but also significant limitations. The development of a new protocol in which a catalyst for formaldehyde decomposition to CO and H₂ is combined with the catalyst of choice for the subsequent asymmetric hydroformylation is described. This enables ATHF reactions that were problematic to be significantly improved. The new method has been used in the synthesis of several key precursors to biologically active molecules.

Original language	English
Journal	Advanced Synthesis & Catalysis
Volume	Early View
Early online date	13 Aug 2019
DOIs	https://doi.org/10.1002/adsc.201900640
Publication status	E-pub ahead of print - 13 Aug 2019

Keywords

Regioselectivity
Hydroformylation
Carbon monoxide surrogates
Asymmetric synthesis
Rhodium

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10.1002/adsc.201900640

Pittaway_2019_ASC_CO-free_AAM
Copyright © 2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version 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/10.1002/adsc.201900640
Accepted author manuscript, 1.54 MB

Enantioselective Carbonylations: New Insights New Catalysts and New Processes using Enantioselective Carbonylations
Clarke, M. (PI) & Buehl, M. (CoI)
EPSRC
1/09/14 → 30/11/17
Project: Standard

Underpinning data: CO-free Enantioselective Hydroformylation of Functionalised Alkenes: Using a Dual Catalyst System to give Improved Selectivity and yield
Pittaway, R. (Contributor), Dingwall, P. (Contributor), Fuentes García, J. A. (Creator) & Clarke, M. L. (Creator), University of St Andrews, 21 Apr 2020
DOI: 10.17630/e491713d-9de2-4fa4-8853-4d7ce2656cfd
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title = "CO-free enantioselective hydroformylation of functionalised alkenes: using a dual catalyst system to give improved selectivity and yield",

abstract = "The scope of carbon monoxide-free Asymmetric Transfer HydroFormylation (ATHF) procedures using a highly active single catalyst system derived from 1,2-bis-((2,5)-diphenylphospholano)ethane as chiral ligand has been studied. This reveals some highly successful reactions, but also significant limitations. The development of a new protocol in which a catalyst for formaldehyde decomposition to CO and H2 is combined with the catalyst of choice for the subsequent asymmetric hydroformylation is described. This enables ATHF reactions that were problematic to be significantly improved. The new method has been used in the synthesis of several key precursors to biologically active molecules.",

keywords = "Regioselectivity, Hydroformylation, Carbon monoxide surrogates, Asymmetric synthesis, Rhodium",

author = "Rachael Pittaway and Paul Dingwall and Jos{\'e} Fuentes and Matt Clarke",

note = "The EPSRC doctoral training grant supported RP (DTG grant: 1518070)). The EPSRC (EP/M003868/1) is also acknowledged for funding (JAF&PD).",

year = "2019",

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doi = "10.1002/adsc.201900640",

language = "English",

volume = "Early View",

journal = "Advanced Synthesis & Catalysis",

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T2 - using a dual catalyst system to give improved selectivity and yield

AU - Pittaway, Rachael

AU - Dingwall, Paul

AU - Fuentes, José

AU - Clarke, Matt

N1 - The EPSRC doctoral training grant supported RP (DTG grant: 1518070)). The EPSRC (EP/M003868/1) is also acknowledged for funding (JAF&PD).

PY - 2019/8/13

Y1 - 2019/8/13

N2 - The scope of carbon monoxide-free Asymmetric Transfer HydroFormylation (ATHF) procedures using a highly active single catalyst system derived from 1,2-bis-((2,5)-diphenylphospholano)ethane as chiral ligand has been studied. This reveals some highly successful reactions, but also significant limitations. The development of a new protocol in which a catalyst for formaldehyde decomposition to CO and H2 is combined with the catalyst of choice for the subsequent asymmetric hydroformylation is described. This enables ATHF reactions that were problematic to be significantly improved. The new method has been used in the synthesis of several key precursors to biologically active molecules.

AB - The scope of carbon monoxide-free Asymmetric Transfer HydroFormylation (ATHF) procedures using a highly active single catalyst system derived from 1,2-bis-((2,5)-diphenylphospholano)ethane as chiral ligand has been studied. This reveals some highly successful reactions, but also significant limitations. The development of a new protocol in which a catalyst for formaldehyde decomposition to CO and H2 is combined with the catalyst of choice for the subsequent asymmetric hydroformylation is described. This enables ATHF reactions that were problematic to be significantly improved. The new method has been used in the synthesis of several key precursors to biologically active molecules.

KW - Regioselectivity

KW - Hydroformylation

KW - Carbon monoxide surrogates

KW - Asymmetric synthesis

KW - Rhodium

U2 - 10.1002/adsc.201900640

DO - 10.1002/adsc.201900640

M3 - Article

SN - 1615-4150

VL - Early View

JO - Advanced Synthesis & Catalysis

JF - Advanced Synthesis & Catalysis

ER -

CO-free enantioselective hydroformylation of functionalised alkenes: using a dual catalyst system to give improved selectivity and yield

Abstract

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Enantioselective Carbonylations: New Insights New Catalysts and New Processes using Enantioselective Carbonylations

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Underpinning data: CO-free Enantioselective Hydroformylation of Functionalised Alkenes: Using a Dual Catalyst System to give Improved Selectivity and yield

Cite this