Single-Face/All-cis Arene Hydrogenation by a Supported Single-Site d0 Organozirconium Catalyst

Madelyn Marie Stalzer; Christopher P. Nicholas; Alak Bhattacharyya; Alessandro Motta; Massimiliano Delferro; Tobin J. Marks

doi:10.1002/anie.201600345

Single-Face/All-cis Arene Hydrogenation by a Supported Single-Site d⁰ Organozirconium Catalyst

Madelyn Marie Stalzer, Christopher P. Nicholas, Alak Bhattacharyya, Alessandro Motta, Massimiliano Delferro, Tobin J. Marks

Chemistry

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

56 Scopus citations

Abstract

The single-site supported organozirconium catalyst Cp∗ZrBz₂/ZrS (Cp∗=Me₅C₅, Bz=benzyl, ZrS=sulfated zirconia) catalyzes the single-face/all-cis hydrogenation of a large series of alkylated and fused arene derivatives to the corresponding all-cis-cyclohexanes. Kinetic/mechanistic and DFT analysis argue that stereoselection involves rapid, sequential H₂ delivery to a single catalyst-bound arene face, versus any competing intramolecular arene π-face interchange. Stereocontrol is on: A single-site supported organozirconium catalyst exhibits unprecedented all-cis stereo/face-selective hydrogenation of substituted alkylarenes under mild reaction conditions. The resulting stereopure cycloalkanes offer new building blocks for value-added fine chemicals.

Original language	English (US)
Pages (from-to)	5263-5267
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	17
DOIs	https://doi.org/10.1002/anie.201600345
State	Published - Apr 18 2016

Funding

Financial support provided by UOP LLC, a Honeywell Company (Des Plaines, IL) and the Division of Chemical Sciences, Office of Basic Energy Sciences, Office of Energy Research, US Department of Energy (Grant DE-FG02-86ER13511). Purchases of NMR and GC-TOF instrumentation at the Integrated Molecular Structure Education and Research Center (IMSERC) of Northwestern Univ. were supported by NSF grants CHE-1048773 and CHE-0923236, respectively. Computational resources were provided by the Northwestern Univ. Quest High Performance Computing cluster (M.D.) and CINECA award HP10CBHAYD 2014 under the ISCRA initiative (A.M.). We thank Dr. J.-C. Bricker of UOP for helpful discussions. A patent application partially based on this work has been filed (US Patent Application 14/559,380 2014).

Keywords

DFT calculations
Organozirconium catalyst
Stereoselective hydrogenation
Sulfated oxides
Supported catalysts

ASJC Scopus subject areas

Catalysis
General Chemistry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/anie.201600345

Cite this

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title = "Single-Face/All-cis Arene Hydrogenation by a Supported Single-Site d0 Organozirconium Catalyst",

abstract = "The single-site supported organozirconium catalyst Cp∗ZrBz2/ZrS (Cp∗=Me5C5, Bz=benzyl, ZrS=sulfated zirconia) catalyzes the single-face/all-cis hydrogenation of a large series of alkylated and fused arene derivatives to the corresponding all-cis-cyclohexanes. Kinetic/mechanistic and DFT analysis argue that stereoselection involves rapid, sequential H2 delivery to a single catalyst-bound arene face, versus any competing intramolecular arene π-face interchange. Stereocontrol is on: A single-site supported organozirconium catalyst exhibits unprecedented all-cis stereo/face-selective hydrogenation of substituted alkylarenes under mild reaction conditions. The resulting stereopure cycloalkanes offer new building blocks for value-added fine chemicals.",

keywords = "DFT calculations, Organozirconium catalyst, Stereoselective hydrogenation, Sulfated oxides, Supported catalysts",

author = "Stalzer, {Madelyn Marie} and Nicholas, {Christopher P.} and Alak Bhattacharyya and Alessandro Motta and Massimiliano Delferro and Marks, {Tobin J.}",

note = "Funding Information: Financial support provided by UOP LLC, a Honeywell Company (Des Plaines, IL) and the Division of Chemical Sciences, Office of Basic Energy Sciences, Office of Energy Research, US Department of Energy (Grant DE-FG02-86ER13511). Purchases of NMR and GC-TOF instrumentation at the Integrated Molecular Structure Education and Research Center (IMSERC) of Northwestern Univ. were supported by NSF grants CHE-1048773 and CHE-0923236, respectively. Computational resources were provided by the Northwestern Univ. Quest High Performance Computing cluster (M.D.) and CINECA award HP10CBHAYD 2014 under the ISCRA initiative (A.M.). We thank Dr. J.-C. Bricker of UOP for helpful discussions. A patent application partially based on this work has been filed (US Patent Application 14/559,380 2014). Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

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AU - Bhattacharyya, Alak

AU - Motta, Alessandro

AU - Delferro, Massimiliano

AU - Marks, Tobin J.

N1 - Funding Information: Financial support provided by UOP LLC, a Honeywell Company (Des Plaines, IL) and the Division of Chemical Sciences, Office of Basic Energy Sciences, Office of Energy Research, US Department of Energy (Grant DE-FG02-86ER13511). Purchases of NMR and GC-TOF instrumentation at the Integrated Molecular Structure Education and Research Center (IMSERC) of Northwestern Univ. were supported by NSF grants CHE-1048773 and CHE-0923236, respectively. Computational resources were provided by the Northwestern Univ. Quest High Performance Computing cluster (M.D.) and CINECA award HP10CBHAYD 2014 under the ISCRA initiative (A.M.). We thank Dr. J.-C. Bricker of UOP for helpful discussions. A patent application partially based on this work has been filed (US Patent Application 14/559,380 2014). Publisher Copyright: © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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N2 - The single-site supported organozirconium catalyst Cp∗ZrBz2/ZrS (Cp∗=Me5C5, Bz=benzyl, ZrS=sulfated zirconia) catalyzes the single-face/all-cis hydrogenation of a large series of alkylated and fused arene derivatives to the corresponding all-cis-cyclohexanes. Kinetic/mechanistic and DFT analysis argue that stereoselection involves rapid, sequential H2 delivery to a single catalyst-bound arene face, versus any competing intramolecular arene π-face interchange. Stereocontrol is on: A single-site supported organozirconium catalyst exhibits unprecedented all-cis stereo/face-selective hydrogenation of substituted alkylarenes under mild reaction conditions. The resulting stereopure cycloalkanes offer new building blocks for value-added fine chemicals.

AB - The single-site supported organozirconium catalyst Cp∗ZrBz2/ZrS (Cp∗=Me5C5, Bz=benzyl, ZrS=sulfated zirconia) catalyzes the single-face/all-cis hydrogenation of a large series of alkylated and fused arene derivatives to the corresponding all-cis-cyclohexanes. Kinetic/mechanistic and DFT analysis argue that stereoselection involves rapid, sequential H2 delivery to a single catalyst-bound arene face, versus any competing intramolecular arene π-face interchange. Stereocontrol is on: A single-site supported organozirconium catalyst exhibits unprecedented all-cis stereo/face-selective hydrogenation of substituted alkylarenes under mild reaction conditions. The resulting stereopure cycloalkanes offer new building blocks for value-added fine chemicals.

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KW - Stereoselective hydrogenation

KW - Sulfated oxides

KW - Supported catalysts

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