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Chapter 26: Alpha-Alkylation by SN1-Type Reactions
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Summary
SN1-Type Nucleophilic Reaction by Generation of Carbocations
Organocatalytic Stereoselective SN1-Type Reactions with Enamine Catalysis
Asymmetric SN1-Type α-Alkylation of Ketones
Combination of Enamine Catalysis and Lewis Acids in SN1-Type Reactions
Organocatalytic SN1-Type Reactions with Brønsted Acids
SN1-Type Reaction Promoted by Chiral Thioureas
SN1-Type Organocatalytic Reaction of Iminium, Oxonium, and Aziridinium Intermediate
Acceleration of oxidation promoted by laccase irradiation with red light
Irradiation with red light is able to improve yields and shorten the reaction time in enzymatic reactions. A commercially available laccase from Trametes versicolor, used in conjunction with a catalytic amount of TEMPO (20 mol%), was irradiated under red light (630 nm) for the clean oxidation of benzylic alcohols and amines in a faster reaction compared to the one conducted in the dark, affording the desired product in excellent yields (up to 99%) using air as the terminal oxidant. The observed acceleration is due to the strongest oxidation ability of laccase, in its excited state, towards TEMPO
Merging Organocatalysis with an Indium(III)-Mediated Process: A Stereoselective α-Alkylation of Aldehydes with Allylic Alcohols
IB
OrganoCATAlytic approaches towards easily synthesized, economical, and high yielding oseltamivir derivatives
Despite widespread immunization, influenza still kills thousand of people, and costs to the US, Europe and Asia enormous amounts of money in terms of healthcare expenses and productivity losses.
While immunization remains an important approach to prevent influenza, small-molecule antiviral agents represent a novel opportunity for an effective prevention and therapy of flu. Inhibitors of neuraminidase (NA), essential enzyme for viral replication in all three classes of influenza viruses, has been recently found. Two of these inhibitors have reached the market, namely zanamivir and oseltamivir phosphate. The recent health concerns related to the avian flu have increased the demand for stockpiles of neuraminidase inhibitors, both as a reasonable frontline therapy against a possible flu pandemic and as a preventive agent. However, natural sources of Shikimic acid are scarce, and the increasing demand have put further pressure to develop new routes that do not involve complex natural products. In addition, there is the need to simplify the synthetic processes and make them less expensive in order to find new drug candidates, cut the drug costs and improve availability as well as efficiency, new chemical synthesis are necessary.
The project proposes a new domino reaction based on an organocatalytic approach to the synthesis of new Tamiflu derivatives. The chemistry involved in this project is easy to perform, and can be well adapted to the industrial context. Moreover, new chemical structures will be prepared and evaluated as potential drug against virulent and mutated flu viruses
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