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Paracyclophane Derivatives in Frustrated Lewis Pair Chemistry

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Frustrated Lewis Pairs II

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 334))

Abstract

The metal-free activation of hydrogen was achieved using [2.2]paracyclophane-derived bisphosphines as Lewis base in frustrated Lewis pair chemistry. The rigid scaffold allows the orientation of functional groups so that steric aspects can be studied without altering the electronic nature. Depending on the geometry, structurally different phosphonium hydridoborates were generated when the frustrated Lewis pairs were exposed to hydrogen. The bisphosphines were applied in the 1,4-hydrosilylation-hydrogenation domino reaction providing access to secondary silyl-protected alcohols from enones in one step. Additionally, the planar-chiral scaffold was applied for the synthesis of novel enantiopure Lewis acids and Lewis bases.

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Abbreviations

Bu:

Butyl

DABCO:

1,4-Diazabicyclo[2.2.2]octane

dppe:

Bis(diphenylphosphino)ethane

dppm:

Bis(diphenylphosphino)methane

dr:

Diastereomer ratio

ee:

Enantiomer excess

equiv.:

Equivalent(s)

Et:

Ethyl

i-Pr:

Isopropyl

L:

Liter(s)

Me:

Methyl

Mes:

Mesityl, 2,4,6-trimethylphenyl

min:

Minute(s)

mol:

Mole(s)

Pc:

[2.2]Paracyclophanyl

Ph:

Phenyl

Pr:

Propyl

r.t.:

Room temperature

s:

Second(s)

s-Bu:

sec-Butyl

t-Bu:

tert-Butyl

THF:

Tetrahydrofuran

TMP:

2,2,6,6-Tetramethylpiperidin

TMS:

Trimethylsilyl

Tol:

4-Methylphenyl

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Authors and Affiliations

  1. Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131, Karlsruhe, Germany

    Lutz Greb & Jan Paradies

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  1. Lutz Greb
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  2. Jan Paradies
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Correspondence to Jan Paradies .

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Editors and Affiliations

  1. Organisch-Chemisches Institut, Universität Münster, Corrensstr. 40, Münster, 48149, Germany

    Gerhard Erker

  2. , Department of Chemistry, University of Toronto, St. George Street 80, Toronto, M5S 3H6, Ontario, Canada

    Douglas W. Stephan

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Greb, L., Paradies, J. (2012). Paracyclophane Derivatives in Frustrated Lewis Pair Chemistry. In: Erker, G., Stephan, D. (eds) Frustrated Lewis Pairs II. Topics in Current Chemistry, vol 334. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2012_375

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