Copper-Catalyzed Aerobic Oxidative Inert CC and CN Bond Cleavage: A New Strategy for the Synthesis of Tertiary Amides

2014 ◽  
Vol 20 (38) ◽  
pp. 12234-12238 ◽  
Author(s):  
Xiuling Chen ◽  
Tieqiao Chen ◽  
Qiang Li ◽  
Yongbo Zhou ◽  
Li-Biao Han ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
New Strategy ◽  
Tertiary Amides

ChemInform Abstract: Copper-Catalyzed Aerobic Oxidative Inert C-C and C-N Bond Cleavage: A New Strategy for the Synthesis of Tertiary Amides.

ChemInform ◽  
2015 ◽  
Vol 46 (11) ◽  
pp. no-no
Author(s):  
Xiuling Chen ◽  
Tieqiao Chen ◽  
Qiang Li ◽  
Yongbo Zhou ◽  
Li-Biao Han ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
New Strategy ◽  
Tertiary Amides

scholarly journals Front Cover: Esterification of Tertiary Amides by Alcohols Through C−N Bond Cleavage over CeO 2 (ChemCatChem 1/2019)

ChemCatChem ◽  
2019 ◽  
Vol 11 (1) ◽  
pp. 1-1 ◽  
Author(s):  
Takashi Toyao ◽  
Md. Nurnobi Rashed ◽  
Yoshitsugu Morita ◽  
Takashi Kamachi ◽  
S. M. A. Hakim Siddiki ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
Front Cover ◽  
Tertiary Amides

scholarly journals A New Strategy for the Synthesis of Tertiary Amides via a Copper-Catalyzed Decyanation Reaction of N,N-Disubstituted 2-Aminomalononitriles

2020 ◽  
Vol 78 (10) ◽  
pp. 1064
Author(s):  
Huan Liang ◽  
Along Gou ◽  
Zhupeng Gao ◽  
Linsheng Lei ◽  
Bowen Wang ◽  
...  
Keyword(s):  
New Strategy ◽  
Tertiary Amides

Cisplatin-Triggered Bioorthogonal Decaging of Amide Bonds for Targeted-Drug Activation in vivo

2018 ◽  
Author(s):  
Benjamin Stenton ◽  
Bruno Oliveira ◽  
João Conde ◽  
Magda Negrão ◽  
Miguel Godinho Ferreira ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
Xenograft Model ◽  
Amide Bonds ◽  
Control Drug ◽  
Tertiary Amide ◽  
Platinum Salts ◽  
First Choice ◽  
Tertiary Amides ◽  
Drug Activation

<p>Creating ways to control drug activation at specific tissues while sparing healthy tissues remains a major challenge. The administration of exogenous triggers offers the possibility for precise and traceless drug activation. However, ensuring localization of the trigger as well as the prodrug at the diseased tissue is complex while essential for therapeutic efficacy and to avoid side-toxicity. Cisplatin remains a first line option to treat 20% of all cancer patients and while clearing after 30 min from blood it concentrates in tumor tissues. Here, we demonstrate the use of the platinum-mediated bond cleavage of protected tertiary amides, which can occur in a catalytic manner under bioorthogonal conditions. Protected analogues of cytotoxic drugs 5-fluorouracil (5-FU) and monomethyl auristatin E (MMAE) were successfully activated using non-toxic amounts of platinum salts in cells. An otherwise fully stable and non-internalizing ADC built using a bifunctional linker featuring a tertiary amide protected MMAE was also bioorthogonally decaged in the presence of platinum salts for extracellular drug release. Finally, cisplatin-mediated activation of a prodrug 5-FU was shown in a colorectal zebrafish xenograft model leading to a significant tumor reduction. Considering cisplatin’s continued use as a first-choice treatment for many solid cancers and especially in colorectal cancer, we anticipate that our platinum-mediated decaging strategy will enhance cancer therapy by allowing tumor specific prodrug activation.</p>

A New Strategy for the Synthesis of Poly-Substituted 3-H, 3-Fluoro, or 3-Trifluoromethyl Pyridines via the Tandem C−F Bond Cleavage Protocol

2010 ◽  
Vol 12 (19) ◽  
pp. 4376-4379 ◽  
Author(s):  
Zixian Chen ◽  
Jiangtao Zhu ◽  
Haibo Xie ◽  
Shan Li ◽  
Yongming Wu ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
New Strategy

Copper-Catalyzed Cleavage of Unstrained C–C Bonds for the Synthesis of 1-Acyloxy-2,2,6,6-tetramethylpiperidines from Cyclic or Acyclic Ketones

Synlett ◽  
2017 ◽  
Vol 28 (16) ◽  
pp. 2163-2168 ◽  
Author(s):  
Wang Zhou ◽  
Qijian Jiang ◽  
Luo Yang
Keyword(s):  
Bond Cleavage ◽  
New Strategy ◽  
Phenanthroline Monohydrate ◽  
Acyclic Ketones

A copper-catalyzed approach for the synthesis of 1-acyloxy-2,2,6,6-tetramethylpiperidines through the C–C bond cleavage of cyclic or acyclic ketones was developed. In this chemistry, a combination of CuCl2·2H2O, 1,10-phenanthroline monohydrate, and aniline was crucial for the formation of the desired products by the reaction of ketones with TEMPO. This research provides a new strategy for the further transformation of α-aryl cyclic or acyclic ketones.

Esterification of Tertiary Amides by Alcohols Through C−N Bond Cleavage over CeO 2

ChemCatChem ◽  
2018 ◽  
Vol 11 (1) ◽  
pp. 449-456 ◽  
Author(s):  
Takashi Toyao ◽  
Md. Nurnobi Rashed ◽  
Yoshitsugu Morita ◽  
Takashi Kamachi ◽  
S. M. A. Hakim Siddiki ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
Tertiary Amides

scholarly journals Reverse Polarity Reductive Functionalization of Tertiary Amides via a Dual Iridium Catalyzed Hydrosilylation & SET Strategy

2020 ◽  
Author(s):  
Tatiana Rogova ◽  
Pablo Gabriel ◽  
Stamatia Zavitsanou ◽  
Jamie Leitch ◽  
Fernanda Duarte ◽  
...  
Keyword(s):  
Active Pharmaceutical Ingredient ◽  
Building Blocks ◽  
Chemical System ◽  
Secondary Amide ◽  
Reductive Activation ◽  
Tertiary Amide ◽  
New Strategy ◽  
Tandem Process ◽  
Electron Reduction ◽  
Tertiary Amides

A new strategy for the mild generation of synthetically valuable α-amino radicals from robust tertiary amide building blocks has been developed. By combining Vaska’s complex-catalyzed tertiary amide reductive activation and photochemical single electron reduction into a streamlined tandem process, metastable hemiaminal intermediates were successfully transformed into nucleophilic α-amino free radical species. This umpolung approach to such reactive intermediates was exemplified through coupling with an electrophilic dehydroalanine acceptor, resulting in the synthesis of an array of α-functionalized tertiary amine derivatives, previously inaccessible from the amide starting materials. The utility of the strategy was expanded to include secondary amide substrates, intramolecular variants and late stage functionalization of an active pharmaceutical ingredient. DFT analyses were used to establish the reaction mechanism and elements of the chemical system that were responsible for the reaction’s efficiency.

Cisplatin-Triggered Bioorthogonal Decaging of Amide Bonds for Targeted-Drug Activation in vivo

2018 ◽  
Author(s):  
Benjamin Stenton ◽  
Bruno Oliveira ◽  
João Conde ◽  
Magda Negrão ◽  
Miguel Godinho Ferreira ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
Xenograft Model ◽  
Amide Bonds ◽  
Control Drug ◽  
Tertiary Amide ◽  
Platinum Salts ◽  
First Choice ◽  
Tertiary Amides ◽  
Drug Activation

<p>Creating ways to control drug activation at specific tissues while sparing healthy tissues remains a major challenge. The administration of exogenous triggers offers the possibility for precise and traceless drug activation. However, ensuring localization of the trigger as well as the prodrug at the diseased tissue is complex while essential for therapeutic efficacy and to avoid side-toxicity. Cisplatin remains a first line option to treat 20% of all cancer patients and while clearing after 30 min from blood it concentrates in tumor tissues. Here, we demonstrate the use of the platinum-mediated bond cleavage of protected tertiary amides, which can occur in a catalytic manner under bioorthogonal conditions. Protected analogues of cytotoxic drugs 5-fluorouracil (5-FU) and monomethyl auristatin E (MMAE) were successfully activated using non-toxic amounts of platinum salts in cells. An otherwise fully stable and non-internalizing ADC built using a bifunctional linker featuring a tertiary amide protected MMAE was also bioorthogonally decaged in the presence of platinum salts for extracellular drug release. Finally, cisplatin-mediated activation of a prodrug 5-FU was shown in a colorectal zebrafish xenograft model leading to a significant tumor reduction. Considering cisplatin’s continued use as a first-choice treatment for many solid cancers and especially in colorectal cancer, we anticipate that our platinum-mediated decaging strategy will enhance cancer therapy by allowing tumor specific prodrug activation.</p>

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