Ni(0)-Catalyzed α-Allylic Alkylation of Regular Ketones with 1,3-Dienes under pH and Redox-neutral Conditions

2019 ◽  
Author(s):  
Tiantian Chen ◽  
Yang Yang ◽  
Liyu Xie ◽  
Haijian Yang ◽  
Guangbin Dong ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Dual Role ◽  
Allylic Alkylation ◽  
Cross Coupling Reaction ◽  
Neutral Conditions

<p>We report a Ni(0)-catalyzed cross coupling reaction between simple ketones and 1,3-dienes. A variety of a-allylic alkylation products were formed in an 1,2-addition manner with excellent regioselectivity. Water was found to significantly accelerate this transformation. A HO-Ni-H species generated from oxidative addition of Ni(0) to H<sub>2</sub>O is proposed to play a “dual role” in activating both the ketone and the diene substrate.</p>

Ni(0)-Catalyzed α-Allylic Alkylation of Regular Ketones with 1,3-Dienes under pH and Redox-neutral Conditions

2019 ◽  
Author(s):  
Tiantian Chen ◽  
Yang Yang ◽  
Liyu Xie ◽  
Haijian Yang ◽  
Guangbin Dong ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Dual Role ◽  
Allylic Alkylation ◽  
Cross Coupling Reaction ◽  
Neutral Conditions

<p>We report a Ni(0)-catalyzed cross coupling reaction between simple ketones and 1,3-dienes. A variety of a-allylic alkylation products were formed in an 1,2-addition manner with excellent regioselectivity. Water was found to significantly accelerate this transformation. A HO-Ni-H species generated from oxidative addition of Ni(0) to H<sub>2</sub>O is proposed to play a “dual role” in activating both the ketone and the diene substrate.</p>

Ni(0)-Catalyzed α-Allylic Alkylation of Regular Ketones with 1,3-Dienes under pH and Redox-neutral Conditions

2018 ◽  
Author(s):  
Tiantian Chen ◽  
Yang Yang ◽  
Liyu Xie ◽  
Haijian Yang ◽  
Guangbin Dong ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Dual Role ◽  
Allylic Alkylation ◽  
Cross Coupling Reaction ◽  
Neutral Conditions

<p>We report a Ni(0)-catalyzed cross coupling reaction between simple ketones and 1,3-dienes. A variety of a-allylic alkylation products were formed in an 1,2-addition manner with excellent regioselectivity. Water was found to significantly accelerate this transformation. A HO-Ni-H species generated from oxidative addition of Ni(0) to H<sub>2</sub>O is proposed to play a “dual role” in activating both the ketone and the diene substrate.</p>

Ni(0)-Catalyzed α-Allylic Alkylation of Regular Ketones with 1,3-Dienes under pH and Redox-neutral Conditions

2019 ◽  
Author(s):  
Tiantian Chen ◽  
Yang Yang ◽  
Liyu Xie ◽  
Haijian Yang ◽  
Guangbin Dong ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Dual Role ◽  
Allylic Alkylation ◽  
Cross Coupling Reaction ◽  
Neutral Conditions

<p>We report a Ni(0)-catalyzed cross coupling reaction between simple ketones and 1,3-dienes. A variety of a-allylic alkylation products were formed in an 1,2-addition manner with excellent regioselectivity. Water was found to significantly accelerate this transformation. A HO-Ni-H species generated from oxidative addition of Ni(0) to H<sub>2</sub>O is proposed to play a “dual role” in activating both the ketone and the diene substrate.</p>

Arenediazonium salts as electrophiles for the oxidative addition of gold(i)

2016 ◽  
Vol 52 (45) ◽  
pp. 7295-7298 ◽  
Author(s):  
Eric Omar Asomoza-Solís ◽  
Jonathan Rojas-Ocampo ◽  
Rubén Alfredo Toscano ◽  
Susana Porcel
Keyword(s):  
Oxidative Addition ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
One Pot ◽  
Cross Coupling Reaction ◽  
Arenediazonium Salts

Arenediazonium salts have been found to behave as efficient electrophiles for the oxidation of gold(i). Starting from anilines, a one pot cross-coupling reaction of anilines with silver acetylides mediated by gold has been developed.

Aldehydes and Ketones Influence Reactivity and Selectivity in Nickel-Catalyzed Suzuki-Miyaura Reactions

2019 ◽  
Author(s):  
Alasdair Cooper ◽  
David Leonard ◽  
Sonia Bajo ◽  
Paul Burton ◽  
David Nelson
Keyword(s):  
Carbonyl Group ◽  
Functional Groups ◽  
Oxidative Addition ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Aryl Halides ◽  
Cross Coupling Reaction ◽  
Site Selectivity ◽  
Aldehydes And Ketones ◽  
The Cross

We show that the energetically-favorable coordination of aldehydes and ketones – but not esters – to nickel(0) during Suzuki-Miyaura reactions can lead either to exquisite selectivity and enhanced reactivity, or to the inhibition<br>of the reaction. Aryl halides where the C-X bond is connected to the same π-system as an aldehyde or ketone functional<br>group undergo unexpectedly rapid oxidative addition, and are selectively cross-coupled during inter- and intramolecular<br>competition reactions. When aldehydes and ketones are present elsewhere, such as in the form of exogenous additives,<br>the cross-coupling reaction is inhibited depending on how strongly the pendant carbonyl group can coordinate to nickel(0). This work advances our understanding of how common functional groups interact with nickel(0) catalysts, and presents synthetic chemists with a tool that can be used to achieve site-selectivity in functionalized molecules. <br>

Aldehydes and Ketones Influence Reactivity and Selectivity in Nickel-Catalyzed Suzuki-Miyaura Reactions

2019 ◽  
Author(s):  
Alasdair Cooper ◽  
David Leonard ◽  
Sonia Bajo ◽  
Paul Burton ◽  
David Nelson
Keyword(s):  
Carbonyl Group ◽  
Functional Groups ◽  
Oxidative Addition ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Aryl Halides ◽  
Cross Coupling Reaction ◽  
Site Selectivity ◽  
Aldehydes And Ketones ◽  
The Cross

We show that the energetically-favorable coordination of aldehydes and ketones – but not esters – to nickel(0) during Suzuki-Miyaura reactions can lead either to exquisite selectivity and enhanced reactivity, or to the inhibition<br>of the reaction. Aryl halides where the C-X bond is connected to the same π-system as an aldehyde or ketone functional<br>group undergo unexpectedly rapid oxidative addition, and are selectively cross-coupled during inter- and intramolecular<br>competition reactions. When aldehydes and ketones are present elsewhere, such as in the form of exogenous additives,<br>the cross-coupling reaction is inhibited depending on how strongly the pendant carbonyl group can coordinate to nickel(0). This work advances our understanding of how common functional groups interact with nickel(0) catalysts, and presents synthetic chemists with a tool that can be used to achieve site-selectivity in functionalized molecules. <br>

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