Diverse Activation Modes in the Hydroboration of Aldehydes and Ketones with Germanium, Tin, and Lead Lewis Pairs

2016 ◽  
Vol 129 (1) ◽  
pp. 339-343 ◽  
Author(s):  
Julia Schneider ◽  
Christian P. Sindlinger ◽  
Sarah M. Freitag ◽  
Hartmut Schubert ◽  
Lars Wesemann
Keyword(s):  
Germanium Tin ◽  
Aldehydes And Ketones ◽  
Lewis Pairs

Diverse Activation Modes in the Hydroboration of Aldehydes and Ketones with Germanium, Tin, and Lead Lewis Pairs

2016 ◽  
Vol 56 (1) ◽  
pp. 333-337 ◽  
Author(s):  
Julia Schneider ◽  
Christian P. Sindlinger ◽  
Sarah M. Freitag ◽  
Hartmut Schubert ◽  
Lars Wesemann
Keyword(s):  
Germanium Tin ◽  
Aldehydes And Ketones ◽  
Lewis Pairs

Reaction of stannylene phosphorus Lewis pairs with dichlorides of germanium, tin and lead – the formation of base stabilized stannyl stannylenes/germylenes and redox reaction with PbCl2

2016 ◽  
Vol 45 (19) ◽  
pp. 8081-8088 ◽  
Author(s):  
K. M. Krebs ◽  
J.-J. Maudrich ◽  
L. Wesemann
Keyword(s):  
Redox Reaction ◽  
Group 14 ◽  
Germanium Tin ◽  
Lewis Pairs

The reaction of intramolecular stannylene phosphorus Lewis pairs with heavier dichlorides of group 14 (GeCl2, SnCl2, PbCl2) is reported.

Auto-Tandem Catalysis with Frustrated Lewis Pairs for Reductive Etherification of Aldehydes and Ketones

2017 ◽  
Vol 56 (19) ◽  
pp. 5217-5221 ◽  
Author(s):  
Mária Bakos ◽  
Ádám Gyömöre ◽  
Attila Domján ◽  
Tibor Soós
Keyword(s):  
Tandem Catalysis ◽  
Frustrated Lewis Pairs ◽  
Aldehydes And Ketones ◽  
Lewis Pairs

Auto-Tandem Catalysis with Frustrated Lewis Pairs for Reductive Etherification of Aldehydes and Ketones

2017 ◽  
Vol 129 (19) ◽  
pp. 5301-5305 ◽  
Author(s):  
Mária Bakos ◽  
Ádám Gyömöre ◽  
Attila Domján ◽  
Tibor Soós
Keyword(s):  
Tandem Catalysis ◽  
Frustrated Lewis Pairs ◽  
Aldehydes And Ketones ◽  
Lewis Pairs

Nickel-Catalyzed Regioselective Hydroalkylation of 1,3-Dienes with Hydrazones

2019 ◽  
Author(s):  
Leiyang Lv ◽  
Dianhu Zhu ◽  
Zihang Qiu ◽  
Jianbin Li ◽  
Chao-Jun Li
Keyword(s):  
Catalytic Method ◽  
Unsaturated Hydrocarbons ◽  
Carbon Nucleophiles ◽  
Aryl Aldehydes ◽  
Aldehydes And Ketones ◽  
Sterically Hindered

Hydroalkylation of unsaturated hydrocarbons with unstablized carbon nucleophiles is difficult and remains a major challenge. The disclosed examples so far mainly focused on the involvement of heteroatom and/or stabilized carbon nucleophiles as efficient reaction partners. Reported here is an unprecedented regioselective nickel-catalyzed hydroalkylation of 1,3-dienes with hydrazones, generated in situ from abundant aryl aldehydes and ketones and acted as both the sources of unstabilized carbanions and hydride. With this strategy, both terminal and sterically hindered internal dienes are hydroalkylated efficiently in a highly selective manner, thus providing a novel and reliable catalytic method to construct challenging C(sp3)-C(sp3) bonds.

Computationally-Guided Investigation of Dual Amine/pi Lewis Acid Catalysts for Direct Additions of Aldehydes and Ketones to Unactivated Alkenes and Alkynes

2020 ◽  
Author(s):  
Eric Greve ◽  
Jacob D. Porter ◽  
Chris Dockendorff
Keyword(s):  
Lewis Acid ◽  
Density Functional ◽  
Acid Catalyst ◽  
Metal Catalyst ◽  
Catalyst Poisoning ◽  
Lewis Acid Catalysts ◽  
Metal Ligands ◽  
Aldehydes And Ketones ◽  
Lewis Acid Catalyst ◽  
Catalyst Systems

Dual amine/pi Lewis acid catalyst systems have been reported for intramolecular direct additions of aldehydes/ketones to unactivated alkynes and occasionally alkenes, but related intermolecular reactions are rare and not presently of significant synthetic utility, likely due to undesired coordination of enamine intermediates to the metal catalyst. We reasoned that bulky metal ligands and bulky amine catalysts could minimize catalyst poisoning and could facilitate certain examples of direct intermolecular additions of aldehyde/ketones to alkenes/alkynes. Density Functional Theory (DFT) calculations were performed that suggested that PyBOX-Pt(II) catalysts for alkene/alkyne activation could be combined with MacMillan’s imidazolidinone organocatalyst for aldehyde/ketone activation to facilitate desirable C-C bond formations, and certain reactions were calculated to be more exergonic than catalyst poisoning pathways. As calculated, preformed enamines generated from the MacMillan imidazolidinone did not displace ethylene from a biscationic (<i>t</i>-Bu)PyBOX-Pt<sup>2+</sup>complex, but neither were the desired C-C bond formations observed under several different conditions.

Computationally-Guided Investigation of Dual Amine/pi Lewis Acid Catalysts for Direct Additions of Aldehydes and Ketones to Unactivated Alkenes and Alkynes

2020 ◽  
Author(s):  
Eric Greve ◽  
Jacob D. Porter ◽  
Chris Dockendorff
Keyword(s):  
Lewis Acid ◽  
Density Functional ◽  
Acid Catalyst ◽  
Metal Catalyst ◽  
Catalyst Poisoning ◽  
Lewis Acid Catalysts ◽  
Metal Ligands ◽  
Aldehydes And Ketones ◽  
Lewis Acid Catalyst ◽  
Catalyst Systems

Dual amine/pi Lewis acid catalyst systems have been reported for intramolecular direct additions of aldehydes/ketones to unactivated alkynes and occasionally alkenes, but related intermolecular reactions are rare and not presently of significant synthetic utility, likely due to undesired coordination of enamine intermediates to the metal catalyst. We reasoned that bulky metal ligands and bulky amine catalysts could minimize catalyst poisoning and could facilitate certain examples of direct intermolecular additions of aldehyde/ketones to alkenes/alkynes. Density Functional Theory (DFT) calculations were performed that suggested that PyBOX-Pt(II) catalysts for alkene/alkyne activation could be combined with MacMillan’s imidazolidinone organocatalyst for aldehyde/ketone activation to facilitate desirable C-C bond formations, and certain reactions were calculated to be more exergonic than catalyst poisoning pathways. As calculated, preformed enamines generated from the MacMillan imidazolidinone did not displace ethylene from a biscationic (<i>t</i>-Bu)PyBOX-Pt<sup>2+</sup>complex, but neither were the desired C-C bond formations observed under several different conditions.

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