scholarly journals Generation of Mixed Anhydrides via Oxidative Fragmentation of Tertiary Cyclopropanols with Phenyliodine(III) Dicarboxylates

Molecules ◽  
2020 ◽  
Vol 26 (1) ◽  
pp. 140
Author(s):  
Dzmitry M. Zubrytski ◽  
Gábor Zoltán Elek ◽  
Margus Lopp ◽  
Dzmitry G. Kananovich
Keyword(s):  
Cyclic Peptide ◽  
Secondary Amines ◽  
Macrocyclic Lactones ◽  
Primary Alcohols ◽  
Diversity Oriented Synthesis ◽  
Bioactive Natural Products ◽  
Deacetylase Inhibitor ◽  
Synthetic Utility ◽  
Mixed Anhydrides ◽  
Last Stage

Oxidative fragmentation of tertiary cyclopropanols with phenyliodine(III) dicarboxylates in aprotic solvents (dichloromethane, chloroform, toluene) produces mixed anhydrides. The fragmentation reaction is especially facile with phenyliodine(III) reagents bearing electron-withdrawing carboxylate ligands (trifluoroacetyl, 2,4,6-trichlorobenzoyl, 3-nitrobenzoyl), and affords 95−98% yields of the corresponding mixed anhydride products. The latter can be straightforwardly applied for the acylation of various nitrogen, oxygen and sulfur-centered nucleophiles (primary and secondary amines, hydroxylamines, primary alcohols, phenols, thiols). Intramolecular acylation yielding macrocyclic lactones can also be performed. The developed transformation has bolstered the synthetic utility of cyclopropanols as pluripotent intermediates in diversity-oriented synthesis of bioactive natural products and their synthetic congeners. For example, it was successfully applied for the last-stage modification of a cyclic peptide to produce a precursor of a known histone deacetylase inhibitor.

4π electrocyclisation in domino processes: contemporary trends and synthetic applications towards natural products

2015 ◽  
Vol 13 (44) ◽  
pp. 10774-10796 ◽  
Author(s):  
Nadeem S. Sheikh
Keyword(s):  
Natural Products ◽  
Domino Reactions ◽  
Bioactive Natural Products ◽  
Mechanistic Insight ◽  
Synthetic Utility

Recent most illustrative examples dealing with 4π electrocyclisation in domino reactions, along with a precise mechanistic insight and its synthetic utility towards bioactive natural products are concisely reviewed.

scholarly journals Diversity-oriented synthesis of analogues of the novel macrocyclic peptide FR-225497 through late stage functionalization

2015 ◽  
Vol 11 ◽  
pp. 2487-2492 ◽  
Author(s):  
Jyotiprasad Mukherjee ◽  
Suman Sil ◽  
Shital Kumar Chattopadhyay
Keyword(s):  
Late Stage ◽  
Histone Deacetylase Inhibitor ◽  
Synthetic Approach ◽  
The Novel ◽  
Diversity Oriented Synthesis ◽  
Cross Metathesis ◽  
Naturally Occurring ◽  
Deacetylase Inhibitor ◽  
Structural Analogues ◽  
Macrocyclic Peptide

A concise synthetic approach to a class of biologically interesting cyclic tetrapeptides is reported which involves a late-stage functionalization of a macrocyclic scaffold through cross metathesis in an attempt to create diversity. The utility of this protocol is demonstrated through the preparation of three structural analogues of the important naturally occurring histone deacetylase inhibitor FR-225497.

Iron-catalysed sequential reaction towards α-aminonitriles from secondary amines, primary alcohols and trimethylsilyl cyanide

2016 ◽  
Vol 52 (13) ◽  
pp. 2776-2779 ◽  
Author(s):  
Hang Shen ◽  
Liangzhen Hu ◽  
Qing Liu ◽  
Muhammad Ijaz Hussain ◽  
Jing Pan ◽  
...  
Keyword(s):  
Secondary Amines ◽  
Primary Alcohols ◽  
Reaction Conditions ◽  
One Pot ◽  
Sequential Reaction ◽  
Trimethylsilyl Cyanide

We developed a one-pot iron-catalysed sequential reaction of secondary amines under mild reaction conditions to give the corresponding α-aminonitriles.

scholarly journals Advances in the Asymmetric Total Synthesis of Natural Products Using Chiral Secondary Amine Catalyzed Reactions of α,β-Unsaturated Aldehydes

Molecules ◽  
2019 ◽  
Vol 24 (18) ◽  
pp. 3412 ◽  
Author(s):  
Zhonglei Wang
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Secondary Amine ◽  
Bioactive Molecules ◽  
Secondary Amines ◽  
Asymmetric Total Synthesis ◽  
Bioactive Natural Products ◽  
Unsaturated Aldehydes ◽  
Target Molecules ◽  
Catalyzed Reactions

Chirality is one of the most important attributes for its presence in a vast majority of bioactive natural products and pharmaceuticals. Asymmetric organocatalysis methods have emerged as a powerful methodology for the construction of highly enantioenriched structural skeletons of the target molecules. Due to their extensive application of organocatalysis in the total synthesis of bioactive molecules and some of them have been used in the industrial synthesis of drugs have attracted increasing interests from chemists. Among the chiral organocatalysts, chiral secondary amines (MacMillan’s catalyst and Jorgensen’s catalyst) have been especially considered attractive strategies because of their impressive efficiency. Herein, we outline advances in the asymmetric total synthesis of natural products and relevant drugs by using the strategy of chiral secondary amine catalyzed reactions of α,β-unsaturated aldehydes in the last eighteen years.

Reactions of 4-phenyl-3H-1,2,4-triazole-3,5 (4H)-dione with alcohols and amines

1979 ◽  
Vol 57 (20) ◽  
pp. 2727-2733 ◽  
Author(s):  
Lê H. Dao ◽  
Donald Mackay
Keyword(s):  
Benzyl Alcohol ◽  
Title Compound ◽  
Secondary Amines ◽  
Secondary Alcohols ◽  
Bicyclic Compound ◽  
Tertiary Amines ◽  
Primary Alcohols ◽  
Complex Products ◽  
Diethyl Azodicarboxylate ◽  
Reaction Compound

Two equivalents of the title compound (1) react with one equivalent of primary alcohols to give good yields of nitrogen and 1-alkoxycarbonyl-2-N-phenylcarbamoyl-4-phenyl-1,2,4-triazolidine-3,5-di ones (3). With secondary alcohols or benzyl alcohol the major products are the ketone or benzaldehyde, while 3 are minor products. The latter can, however, be made the major products if pyridine is used to catalyze the reaction. Compound 3a dissociates on heating or in pyridine solution into the 1-methoxycarbonyltriazolidinedione 4.If alcohols are absent 1 is converted by pyridine or other tertiary amines into nitrogen and the bicyclic compound 9; if diethyl azodicarboxylate is present in the reaction compound 13 can be trapped.Primary and secondary amines react very rapidly with 1 to give nitrogen and complex products. It is likely that these are 1,2-dicarbamoyl-4-phenyltriazolidine diones, analogous to 3, and that they are very prone to dissociate in solution.

ChemInform Abstract: Iron-Catalyzed Sequential Reaction Towards α-Aminonitriles from Secondary Amines, Primary Alcohols and Trimethylsilyl Cyanide.

ChemInform ◽  
2016 ◽  
Vol 47 (24) ◽  
Author(s):  
Hang Shen ◽  
Liangzhen Hu ◽  
Qing Liu ◽  
Muhammad Ijaz Hussain ◽  
Jing Pan ◽  
...  
Keyword(s):  
Secondary Amines ◽  
Primary Alcohols ◽  
Sequential Reaction ◽  
Trimethylsilyl Cyanide
Sign in / Sign up

Export Citation Format

Share Document