Markovnikov versus anti-Markovnikov hydrophosphination: Divergent reactivity using an iron(II) β-diketiminate pre-catalyst

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Abstract

The ability to tune between different regioselectivities using a common pre-catalyst is an unusual yet highly desirable process. Here, we report the use of an iron(II) pre-catalyst that can be used to synthesize vinyl phosphines in a Markovnikov-selective manner in benzene, whereas a simple change to dichloromethane as the reaction solvent leads to the Z-selective anti-Markovnikov product. Preliminary mechanistic studies are reported that suggest Markovnikov selectivity is a radical-mediated process, whereas the anti-Markovnikov selectivity is not radical in nature but is due to a change in oxidation state.
LanguageEnglish
Pages9039-9043
JournalChemistry - A European Journal
Volume23
Issue number38
Early online date19 Jun 2017
DOIs
StatusPublished - 6 Jul 2017

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Iron
Phosphines
Regioselectivity
Catalysts
Methylene Chloride
Benzene
Oxidation

Cite this

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title = "Markovnikov versus anti-Markovnikov hydrophosphination: Divergent reactivity using an iron(II) β-diketiminate pre-catalyst",
abstract = "The ability to tune between different regioselectivities using a common pre-catalyst is an unusual yet highly desirable process. Here, we report the use of an iron(II) pre-catalyst that can be used to synthesize vinyl phosphines in a Markovnikov-selective manner in benzene, whereas a simple change to dichloromethane as the reaction solvent leads to the Z-selective anti-Markovnikov product. Preliminary mechanistic studies are reported that suggest Markovnikov selectivity is a radical-mediated process, whereas the anti-Markovnikov selectivity is not radical in nature but is due to a change in oxidation state.",
author = "Andrew King and Kimberley Gallagher and Mahon, {Mary F.} and Webster, {Ruth L.}",
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T1 - Markovnikov versus anti-Markovnikov hydrophosphination: Divergent reactivity using an iron(II) β-diketiminate pre-catalyst

AU - King, Andrew

AU - Gallagher, Kimberley

AU - Mahon, Mary F.

AU - Webster, Ruth L.

PY - 2017/7/6

Y1 - 2017/7/6

N2 - The ability to tune between different regioselectivities using a common pre-catalyst is an unusual yet highly desirable process. Here, we report the use of an iron(II) pre-catalyst that can be used to synthesize vinyl phosphines in a Markovnikov-selective manner in benzene, whereas a simple change to dichloromethane as the reaction solvent leads to the Z-selective anti-Markovnikov product. Preliminary mechanistic studies are reported that suggest Markovnikov selectivity is a radical-mediated process, whereas the anti-Markovnikov selectivity is not radical in nature but is due to a change in oxidation state.

AB - The ability to tune between different regioselectivities using a common pre-catalyst is an unusual yet highly desirable process. Here, we report the use of an iron(II) pre-catalyst that can be used to synthesize vinyl phosphines in a Markovnikov-selective manner in benzene, whereas a simple change to dichloromethane as the reaction solvent leads to the Z-selective anti-Markovnikov product. Preliminary mechanistic studies are reported that suggest Markovnikov selectivity is a radical-mediated process, whereas the anti-Markovnikov selectivity is not radical in nature but is due to a change in oxidation state.

UR - https://doi.org/10.1002/chem.201702374

U2 - 10.1002/chem.201702374

DO - 10.1002/chem.201702374

M3 - Article

VL - 23

SP - 9039

EP - 9043

JO - Chemistry - A European Journal

T2 - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

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ER -