Methoxide‐Enabled Zirconium‐Catalyzed Migratory Alkene Hydrosilylation DOI Creative Commons
Orsola A. Luongo, Miran Lemmerer,

Sanne L. Albers

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(46)

Published: July 24, 2024

Abstract A zirconocene dichloride‐catalyzed alkene hydrosilylation is reported that can be applied to non‐activated and conjugated terminal internal alkenes. It involves a catalytic Zr‐walk process leads selective conversion the linear product. Lithium methoxide serves as mild catalyst activating agent, which significantly increases applicability operational simplicity in comparison earlier zirconium(II)‐based protocols. Supported by additional experiments calculations, mechanism via zirconium(IV) intermediates proposed. Due benign nature ready‐availability of zirconium catalyst, reaction an attractive alternative established methods.

Language: Английский

Mild Divergent Semireductive Transformations of Secondary and Tertiary Amides via Zirconocene Hydride Catalysis DOI Creative Commons

Rebecca A. Kehner,

Ge Zhang, Liela Bayeh-Romero

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(9), P. 4921 - 4927

Published: Feb. 21, 2023

The mild catalytic partial reduction of amides to imines has proven be a challenging synthetic transformation, with many transition metals directly reducing these substrates amines. Herein, we report mild, method for the semireduction both secondary and tertiary via zirconocene hydride catalysis. Utilizing just 5 mol % Cp

Language: Английский

Citations

14
Zirconium Hydride Catalysis Initiated by Tetrabutylammonium Fluoride DOI Creative Commons
Stephen J. Harwood, Athenea N. Aloiau,

Briana M. Bobek

et al.

Published: May 10, 2024

In our drug discovery campaigns to target the oncogenic drivers of cancers, demand for a chemoselective, stereoselective and economical synthesis chiral benzylamines drove development catalytic zirconium hydride reduction. This methodology uses inexpensive, bench stable zirconocene dichloride, novel tetrabutylammonium fluoride activa-tion tactic catalytically generate metal under ambient conditions. The diastereo- chemoselectivity this reaction was tested with preparation key intermediates from programs in scope sulfinyl ketimines carbonyls relevant medicinal chemistry natural product synthesis. A preliminary mechanistic investi-gation conducted into role indicates that formation occurs initiate catalysis. implications convenient activation approach may provide expanded roles hy-drides transformations.

Language: Английский

Citations

1
Methoxide‐Enabled Zirconium‐Catalyzed Migratory Alkene Hydrosilylation DOI Creative Commons
Orsola A. Luongo, Miran Lemmerer,

Sanne L. Albers

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: July 24, 2024

A zirconocene dichloride-catalyzed alkene hydrosilylation is reported that can be applied to non-activated and conjugated terminal internal alkenes. It involves a catalytic Zr-walk process leads selective conversion the linear product. Lithium methoxide serves as mild catalyst activating agent, which significantly increases applicability operational simplicity in comparison earlier zirconium(II)-based protocols. Supported by additional experiments calculations, mechanism via zirconium(IV) intermediates proposed. Due benign nature ready-availability of zirconium catalyst, reaction an attractive alternative established methods.

Language: Английский

Citations

1
Direct conversion of esters to imines/enamines and applications to polyester waste upcycling DOI Creative Commons

Rebecca A. Kehner,

Weiheng Huang,

Liela Bayeh-Romero

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

The direct conversion of esters to imines or enamines is achieved using zirconocene hydride (ZrH) catalysis. This transformation occurs through an amine-interrupted reduction, bypassing traditional pathways leading alcohol products.

Language: Английский

Citations

1
ZrH-Catalyzed Semi-Reduction of Esters Enabled by an Imine/Enamine Trap DOI Creative Commons

Rebecca A. Kehner,

Liela Bayeh-Romero

Published: Jan. 4, 2024

Semi-reductive transformations of esters remains an underdeveloped but valuable class functional group interconversions. For example, few strategies exist for the catalytic partial reduction to aldehydes, and direct semi-reductive imination/enamination is absent from synthetic strategy. Here, we describe development a highly selective method interconversion imines, enamines, aldehydes or amines through amine-intercepted ZrH-catalyzed reduction. This protocol employs Cp2ZrCl2 as inexpensive catalyst in combination with hydrosilanes simple unprotected amines. The situ formation imines enamines effectively preserves aldehyde oxidation level throughout course reaction. A variety aryl aliphatic are directly transformed up 99% yield 84% yield, little-to-no corresponding alcohols. utility this efficient preparation nitrogen-containing products also presented, including single-flask multicomponent reactions reductive amination esters. These findings further demonstrate oxophilicity-driven ZrH catalysis unconventional chemical transformations.

Language: Английский

Citations

1
Zirconium Hydride Catalysis Initiated by Tetrabutylammonium Fluoride DOI
Athenea N. Aloiau,

Briana M. Bobek,

Kelly E. Pearson

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(16), P. 11525 - 11536

Published: July 29, 2024

In our drug discovery campaigns to target the oncogenic drivers of cancers, demand for a chemoselective, stereoselective and economical synthesis chiral benzylamines drove development catalytic zirconium hydride reduction. This methodology uses inexpensive, bench stable zirconocene dichloride, novel tetrabutylammonium fluoride activation tactic catalytically generate metal under ambient conditions. The diastereo- chemoselectivity this reaction was tested with preparation key intermediates from programs in scope sulfinyl ketimines carbonyls relevant medicinal chemistry natural product synthesis. A preliminary mechanistic investigation conducted into role indicates that formation occurs initiate catalysis. implications convenient approach may provide expanded roles hydrides transformations.

Language: Английский

Citations

1
Selective Transformations Mediated by Group 4 Metal Cyclopentadienyl Complexes DOI
J. Pinkas, Martin Lamač

Topics in organometallic chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 117 - 160

Published: Jan. 1, 2024

Language: Английский

Citations

0
Facile approach towards terminal olefins from esters using Corey-Chaykovsky’s reagents DOI

hucheng shi,

Guoren Yue,

Pen-Ji Yan

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(25), P. 5093 - 5096

Published: Jan. 1, 2024

A new synthetic method for terminal olefins was developed through the reaction of Corey–Chaykovsky reagent with readily available esters. mechanism involving nucleophilic addition, elimination and rearrangement is supported by DFT calculations.

Language: Английский

Citations

0
Methoxide‐Enabled Zirconium‐Catalyzed Migratory Alkene Hydrosilylation DOI Creative Commons
Orsola A. Luongo, Miran Lemmerer,

Sanne L. Albers

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(46)

Published: July 24, 2024

Abstract A zirconocene dichloride‐catalyzed alkene hydrosilylation is reported that can be applied to non‐activated and conjugated terminal internal alkenes. It involves a catalytic Zr‐walk process leads selective conversion the linear product. Lithium methoxide serves as mild catalyst activating agent, which significantly increases applicability operational simplicity in comparison earlier zirconium(II)‐based protocols. Supported by additional experiments calculations, mechanism via zirconium(IV) intermediates proposed. Due benign nature ready‐availability of zirconium catalyst, reaction an attractive alternative established methods.

Language: Английский

Citations

0