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      New Developments of the Principle of Vinylogy as Applied to π-Extended Enolate-Type Donor Systems

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      , , ,
      Chemical Reviews
      American Chemical Society

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          Abstract

          The principle of vinylogy states that the electronic effects of a functional group in a molecule are possibly transmitted to a distal position through interposed conjugated multiple bonds. As an emblematic case, the nucleophilic character of a π-extended enolate-type chain system may be relayed from the legitimate α-site to the vinylogous γ, ε, ..., ω remote carbon sites along the chain, provided that suitable HOMO-raising strategies are adopted to transform the unsaturated pronucleophilic precursors into the reactive polyenolate species. On the other hand, when “unnatural” carbonyl ipso-sites are activated as nucleophiles (umpolung), vinylogation extends the nucleophilic character to “unnatural” β, δ, ... remote sites. Merging the principle of vinylogy with activation modalities and concepts such as iminium ion/enamine organocatalysis, NHC-organocatalysis, cooperative organo/metal catalysis, bifunctional organocatalysis, dicyanoalkylidene activation, and organocascade reactions represents an impressive step forward for all vinylogous transformations. This review article celebrates this evolutionary progress, by collecting, comparing, and critically describing the achievements made over the nine year period 2010–2018, in the generation of vinylogous enolate-type donor substrates and their use in chemical synthesis.

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          Organocatalytic cascade reactions as a new tool in total synthesis.

          The total synthesis of natural products and biologically active compounds, such as pharmaceuticals and agrochemicals, has reached an extraordinary level of sophistication. We are, however, still far away from the 'ideal synthesis' and the state of the art is still frequently hampered by lengthy protecting-group strategies and costly purification procedures derived from the step-by-step protocols. In recent years several new criteria have been brought forward to solve these problems and to improve total synthesis: atom, step and redox economy or protecting-group-free synthesis. Over the past decade the research area of organocatalysis has rapidly grown to become a third pillar of asymmetric catalysis standing next to metal and biocatalysis, thus paving the way for a new and powerful strategy that can help to address these issues - organocatalytic cascade reactions. In this Review we present the first applications of such asymmetric organocascade reactions to the total synthesis of natural products.
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            “On Water”: Unique Reactivity of Organic Compounds in Aqueous Suspension

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              Lewis Base Catalysis in Organic Synthesis

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                Author and article information

                Journal
                Chem Rev
                Chem Rev
                cr
                chreay
                Chemical Reviews
                American Chemical Society
                0009-2665
                1520-6890
                10 February 2020
                11 March 2020
                : 120
                : 5
                : 2448-2612
                Affiliations
                [1]Dipartimento di Scienze degli Alimenti e del Farmaco, Università di Parma , Parco Area delle Scienze 27A, 43124 Parma, Italy
                Author notes
                [* ]Email: franca.zanardi@ 123456unipr.it ; Phone: +39 0521 905067.
                Article
                10.1021/acs.chemrev.9b00481
                7993750
                32040305
                74a9b71f-0e7d-40b6-ab39-055b9906f6c6

                Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained ( https://creativecommons.org/licenses/by/4.0/).

                History
                : 31 July 2019
                Categories
                Review
                Custom metadata
                cr9b00481
                cr9b00481

                Chemistry
                Chemistry

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