Enantio- and Diastereoselective Catalytic Alkylation Reactions with Aziridines

2008 ◽  
Vol 130 (31) ◽  
pp. 10076-10077 ◽  
Author(s):  
Thomas A. Moss ◽  
David R. Fenwick ◽  
Darren J. Dixon
Keyword(s):  
Catalytic Alkylation ◽  
Alkylation Reactions

ChemInform Abstract: Bismuth Salts in Catalytic Alkylation Reactions

ChemInform ◽  
2013 ◽  
Vol 44 (42) ◽  
pp. no-no
Author(s):  
Magnus Rueping ◽  
Boris J. Nachtsheim
Keyword(s):  
Catalytic Alkylation ◽  
Bismuth Salts ◽  
Alkylation Reactions

Catalytic alkylation reactions of weakly acidic carbonyl and related compounds using alkenes as electrophiles

2018 ◽  
Vol 16 (33) ◽  
pp. 5969-5972 ◽  
Author(s):  
Yasuhiro Yamashita ◽  
Ryo Igarashi ◽  
Hirotsugu Suzuki ◽  
Shū Kobayashi
Keyword(s):  
Catalytic Alkylation ◽  
Alkylation Reactions ◽  
Related Compounds

Catalytic alkylation reactions of weakly acidic carbonyl and related pronucleophiles such as amides, esters, and sulfonamides with substituted alkenes have been reported.

ChemInform Abstract: Enantio- and Diastereoselective Catalytic Alkylation Reactions with Aziridines.

ChemInform ◽  
2008 ◽  
Vol 39 (50) ◽  
Author(s):  
Thomas A. Moss ◽  
David R. Fenwick ◽  
Darren J. Dixon
Keyword(s):  
Catalytic Alkylation ◽  
Alkylation Reactions

Deciphering the Redox Chain Mechanism in the Catalytic Alkylation of Quinones

Synlett ◽  
2018 ◽  
Vol 29 (14) ◽  
pp. 1807-1813 ◽  
Author(s):  
Zhi Li ◽  
Xiao-Long Xu
Keyword(s):  
Reaction Mechanism ◽  
Lewis Acid ◽  
Kinetic Studies ◽  
Chain Mechanism ◽  
Chain Reaction ◽  
Catalytic Alkylation ◽  
Redox Chain ◽  
Strong Lewis Acid ◽  
Acid Catalyzed ◽  
Alkylation Reactions

Alkylation of p-quinones with allylic and benzylic esters is achieved by using a strong Lewis acid as the catalyst. This transformation likely follows an unusual redox chain mechanism. In this mechanism, quinone undergoes a sequence of reactions: it is reduced to ­hydroquinone (HQ), functionalized in a Lewis acid-catalyzed Friedel–Crafts alkylation, and then oxidized back to quinone. The last step is concurrent with the first step of a second quinone molecule, which is reduced to new HQ and functionalized, and thus propagates the redox chain reaction. The autoinitiation mechanism of the redox chain is not well understood, but additive HQ or Hantzsch ester can serve as effective initiators. The likelihood of this mechanism was elaborated by ­kinetic studies and various control experiments.1 Introduction2 Discovery of Catalytic Alkylation Reactions of Quinones3 Proposed Redox Chain Reaction Mechanism and Experimental Evidence4 Substrate Scope5 Conclusion

Copper Catalyzed sp3 C-H α-Acetylation

2019 ◽  
Author(s):  
Otome Okoromoba ◽  
Eun Sil Jang ◽  
Claire McMullin ◽  
Thomas Cundari ◽  
Timothy H. Warren
Keyword(s):  
Natural Products ◽  
Dft Studies ◽  
Alkyl Radicals ◽  
Important Chemical ◽  
Alkyl Electrophiles ◽  
Synthetic Intermediates ◽  
Alkylation Reactions

<p>α-substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in in natural products and pharmaceuticals. We report the sp<sup>3</sup> C-H α-acetylation of sp<sup>3</sup> C-H substrates R-H with arylmethyl ketones ArC(O)Me to provide α-alkylated ketones ArC(O)CH<sub>2</sub>R at RT with <sup>t</sup>BuOO<sup>t</sup>Bu as oxidant via copper(I) β-diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α-substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [Cu<sup>II</sup>](CH<sub>2</sub>C(O)Ar) that capture alkyl radicals R• to give R-CH<sub>2</sub>C(O)Ar under competing dimerization of the copper(II) enolate to give the 1,4-diketone ArC(O)CH<sub>2</sub>CH<sub>2</sub>C(O)Ar.</p>

Copper Catalyzed sp3 C-H α-Acetylation

2019 ◽  
Author(s):  
Otome Okoromoba ◽  
Eun Sil Jang ◽  
Claire McMullin ◽  
Thomas Cundari ◽  
Timothy H. Warren
Keyword(s):  
Natural Products ◽  
Dft Studies ◽  
Alkyl Radicals ◽  
Important Chemical ◽  
Alkyl Electrophiles ◽  
Synthetic Intermediates ◽  
Alkylation Reactions

<p>α-substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in in natural products and pharmaceuticals. We report the sp<sup>3</sup> C-H α-acetylation of sp<sup>3</sup> C-H substrates R-H with arylmethyl ketones ArC(O)Me to provide α-alkylated ketones ArC(O)CH<sub>2</sub>R at RT with <sup>t</sup>BuOO<sup>t</sup>Bu as oxidant via copper(I) β-diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α-substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [Cu<sup>II</sup>](CH<sub>2</sub>C(O)Ar) that capture alkyl radicals R• to give R-CH<sub>2</sub>C(O)Ar under competing dimerization of the copper(II) enolate to give the 1,4-diketone ArC(O)CH<sub>2</sub>CH<sub>2</sub>C(O)Ar.</p>

An Anthrone-Based Kv7.2/7.3 Channel Blocker with Improved Properties for the Investigation of Psychiatric and Neurodegenerative Disorders

2019 ◽  
Author(s):  
Jacob Porter ◽  
Oscar Vivas-Rodriguez ◽  
C. David Weaver ◽  
Eamonn Dickson ◽  
Abdulmohsen Alsafran ◽  
...  
Keyword(s):  
Patch Clamp ◽  
Neurodegenerative Disorders ◽  
Channel Blocker ◽  
Optimal Combination ◽  
Channel Blockers ◽  
Enolate Alkylation ◽  
Cyp Inhibition ◽  
Alkylation Reactions ◽  
Metabolic Instability

A set of novel Kv7.2/7.3 (KCNQ2/3) channel blockers was synthesized to address several liabilities of the known compounds XE991 (metabolic instability and CYP inhibition) and the clinical compound DMP 543 (acid instability, insolubility, and lipophilicity). Using the anthrone scaffold of the prior channel blockers, alternative heteroarylmethyl substituents were installed via enolate alkylation reactions. Incorporation of a pyridazine and a fluorinated pyridine gave an analog (JDP-107) with an optimal combination of potency (IC<sub>50</sub>= 0.16 𝜇M in a Kv7.2 thallium flux assay), efficacy in a Kv7.2/7.3 patch clamp assay, and drug-like properties.

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