16790-82-2

Upstream product

• 768-95-6 1-adamanthanol 
• 103-81-1 Benzeneacetamide 
• 140-29-4 phenylacetonitrile 
• 828-51-3 1-Adamantanecarboxylic acid 
• 103-82-2 phenylacetic acid 
• 768-94-5 1-Adamantanamine 
• 103-80-0 phenylacetyl chloride 
• 281-23-2 adamantane 
• 768-90-1 1-Adamantyl bromide 

Relevant academic research and scientific papers

Hindered dialkyl ether synthesis with electrogenerated carbocations

Hindered ethers are of high value for various applications; however, they remain an underexplored area of chemical space because they are difficult to synthesize via conventional reactions1,2. Such motifs are highly coveted in medicinal chemistry, because extensive substitution about the ether bond prevents unwanted metabolic processes that can lead to rapid degradation in vivo. Here we report a simple route towards the synthesis of hindered ethers, in which electrochemical oxidation is used to liberate high-energy carbocations from simple carboxylic acids. These reactive carbocation intermediates, which are generated with low electrochemical potentials, capture an alcohol donor under non-acidic conditions; this enables the formation of a range of ethers (more than 80 have been prepared here) that would otherwise be difficult to access. The carbocations can also be intercepted by simple nucleophiles, leading to the formation of hindered alcohols and even alkyl fluorides. This method was evaluated for its ability to circumvent the synthetic bottlenecks encountered in the preparation of 12 chemical scaffolds, leading to higher yields of the required products, in addition to substantial reductions in the number of steps and the amount of labour required to prepare them. The use of molecular probes and the results of kinetic studies support the proposed mechanism and the role of additives under the conditions examined. The reaction manifold that we report here demonstrates the power of electrochemistry to access highly reactive intermediates under mild conditions and, in turn, the substantial improvements in efficiency that can be achieved with these otherwise-inaccessible intermediates.

Synthesis of N-(Adamantan-1-yl)carbamides by Ritter Reaction from Adamantan-1-ol and Nitriles in the Presence of Cu-Catalysts

A selective synthesis of (Z)-N-(adamantan-1-yl)carbamides by the reaction of adamantan-1-ol and nitriles in the presence of Cu catalysts was carried out. Z-Conformation of amides is established basing on X-ray diffraction analysis and 2D NMR data.

Synthesis and identification of small molecules that potently induce apoptosis in melanoma cells through G1 cell cycle arrest

Late-stage malignant melanoma is a cancer that is refractory to current chemotherapeutic treatments. The average survival time for patients with such a diagnosis is 6 months. In general, the vast majority of anticancer drugs operate through induction of cell cycle arrest and cell death in either the DNA synthesis (S) or mitosis (M) phase of the cell cycle. Unfortunately, the same mechanisms that melanocytes possess to protect cells from DNA damage often confer resistance to drugs that derive their toxicity from S or M phase arrest. Described herein is the synthesis of a combinatorial library of potential proapoptotic agents and the subsequent identification of a class of small molecules (triphenylmethylamides, TPMAs) that arrest the growth of melanoma cells in the G1 phase of the cell cycle. Several of these TPMAs are quite potent inducers of apoptotic death in melanoma cell lines (IC50 ～ 0.5 μM), and importantly, some TPMAs are comparatively nontoxic to normal cells isolated from the bone marrow of healthy donors. Furthermore, the TPMAs were found to dramatically reduce the level of active nuclear factor κ-B (NFκB) in the cell; NFκB is known to be constitutively active in melanoma, and this activity is critical for the proliferation of melanoma cells and their evasion of apoptosis. Compounds that reduce the level of NFκB and arrest cells in the G1 phase of the cell cycle can provide insights into the biology of melanoma and may be effective antimelanoma agents.

Adamantylation and adamantylalkylation of amides, nitriles, and ureas in trifluoroacetic acid

A new preparative procedure was developed for N-adamantylation of carboxylic acids amides and ureas, and C5-adamantylation of barbituric acid in trifluoroacetic acid medium with tertiary adamantanols and 1-adamantylalkanols. The reaction of 2-adamantanols and secondary 1-adamantylalkanols with nitriles was for the first time used in the preparation of W-(2-adamantyl)-and N-(1-adamantylalkyl)amides.

Adamantylation and adamantylalkylation of amides, nitriles and ureas in trifluoroacetic acid

A new preparative method for N-adamantylation of carboxylic acid amides, ureas and for C5-adamantylation of barbituric acid in trifluoroacetic acid (TFA) is proposed. Tertiary 1-adamantanols and 1-(1-adamantyl)alkanols were used as adamantylating agents. The reaction of 1-(1-adamantyl)alkanols with nitriles in TFA solution was employed for the first time for the preparation of N-[1-(1-adamantyl)alkyl]amides.

DERIVATIVES OF ADAMANTANE. II. USE OF TRIFLUOROACETIC ACID IN THE RITTER REACTION

For the case of 1-substituted adamantanes it was possible to realize the synthesis of amides by the Ritter reaction with high yields using trifluoroacetic acid as catalyst and solvent.This makes it possible to realize the process in a homogenous phase and to remove the excess of the nitrile and the excess of the acid itself from the reaction mass by hydrolysis of the intermediate immonium comples.On account of the mild conditions labile nitriles and aminonitriles, in particular, can be used in the reaction.