Refernces
10.1016/S0040-4039(00)95344-9
The research explores the unexpected electrooxidations of aromatic enol ethers in the presence of non-conventional nucleophiles. The study aims to understand the influence of different bases on the outcomes of electrooxidation reactions, specifically focusing on the behavior of 1,2,2-triphenyl-1-methoxyethylene. The researchers found that the electrooxidation process can lead to either substitution or addition reactions, depending on the base used. For instance, when lutidine was used, the reaction exclusively produced N-substituted lutidinium salts, while the use of K2CO3 as a base resulted in anodic addition and the formation of a cyclic carbonate.
10.1002/anie.201906978
The research investigates the reactivity of a mononuclear high-spin iron(III)-alkylperoxo intermediate, [FeIII(t-BuLUrea)(OOCm)(OH2)]2+, generated from the iron(II) complex [FeII(t-BuLUrea)(H2O)(OTf)](OTf) using cumyl hydroperoxide (CmOOH). The study aims to understand the selective and catalytic oxygenation of C-H and C=C bonds in hydrocarbons by this intermediate, particularly focusing on the role of urea groups in the supporting ligand and the influence of a base, 2,6-lutidine. The researchers found that the intermediate exhibits high chemoselectivity and stereoselectivity in oxygenating strong C-H bonds of aliphatic substrates in the presence of 2,6-lutidine, which assists in the heterolytic O-O bond cleavage of the metal-bound alkylperoxo, leading to a reactive metal-based oxidant. The study concludes that the urea groups and the base are crucial in directing the selective and catalytic oxygenation, achieving turnover numbers (TONs) of up to 37 for cyclohexanol in optimized conditions. The findings highlight the importance of ligand design and base promotion in enhancing the reactivity and selectivity of iron-based oxidation catalysts.
10.1021/jo00822a019
The research explores the conversion of 1,3-dithiane derivatives to carbonyl compounds through oxidative hydrolysis using N-halosuccinimide reagents. The study aims to develop specific and effective procedures for this conversion, which is significant in the synthesis and interconversion of monocarbonyl and 1,3-dicarbonyl compounds. The researchers found that mercury(II)-promoted hydrolysis is effective for 2,2-dialkyl derivatives but less so for 2-monoalkyl and 2-acyl derivatives. To address this, they devised three N-halosuccinimide reagents—N-bromosuccinimide alone, N-bromosuccinimide with silver ion, and N-chlorosuccinimide with silver ion—which efficiently hydrolyze 2-acyl-1,3-dithianes to 1,2-dicarbonyl compounds, significantly extending the synthetic utility of the lithiodithiane method. The study concludes that these reagents, particularly N-chlorosuccinimide with silver ion, are advantageous for unsaturated dithianes as they do not affect olefinic linkages, and they can be buffered with 2,6-lutidine or 2,4,6-collidine for acid-sensitive substrates, yielding aldehydes and ketones in high percentages (70-100%).
10.1002/bkcs.11755
The study presents a synthetic method for the preparation of ethyl 4-(alkyl or arylsulfonamido)-2-naphthoates, which are derivatives of 1-aminonaphthalene, 3-aminobenzofuran, and 3-aminobenzothiophene. These compounds are significant due to their presence in biologically active molecules used in cancer treatment and as inhibitors for various enzymes. The synthesis involves a copper(I)-catalyzed cyclization reaction of ethyl (E)-α-ethynyl-β-aryl-α,β-unsaturated esters with N-sulfonyl azides in the presence of 2,6-lutidine in THF at 60°C for 3 hours. This method efficiently produces a wide range of the aforementioned derivatives with the release of molecular nitrogen. The chemicals used in the study include ethyl (E)-α-ethynyl-β-aryl-α,β-unsaturated esters as starting materials, N-sulfonyl azides as reactants, 2,6-lutidine as a base, and copper(I) as a catalyst, all serving specific roles in the cyclization reaction to form the desired aminonaphthalene and related derivatives.
10.1039/c39870000081
The research details the preparation of penicillin-2-carboxylate systems and their conversion into 2-methylene penam and 2-methyl penem systems through a decarboxylative Pummerer reaction. The purpose of this study was to synthesize the 2-exomethylene penam system, which serves as a structural bridge between penicillin and clavulanic acid, and was previously unknown. The researchers successfully synthesized this system and demonstrated its conversion to other penicillin derivatives. Key chemicals used in the process included penicillin V, various oxidants, dimethyl sulphoxide (DMSO), oxalyl chloride, pyridine, 2,6-lutidine, molecular sieves, and phosphorus tribromide in dimethylformamide (DMF). The conclusions drawn from the study indicated that the synthesized compounds, including the 2-exomethylene penam system and the dicarboxylate (12), showed comparable antibacterial activity to penicillin V, while the amide (21) exhibited an order of magnitude lower in activity.