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      Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis

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          Abstract

          Olefin metathesis has made a significant impact on modern organic chemistry, but important shortcomings remain: for example, the lack of efficient processes that can be used to generate acyclic alkenyl halides. Halo-substituted ruthenium carbene complexes decompose rapidly or deliver low activity and/or minimal stereoselectivity, and our understanding of the corresponding high-oxidation-state systems is very limited. In this manuscript, we show that previously unknown halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of an in situ-generated catalyst with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents and proceed to high conversion at ambient temperature within four hours. Many alkenyl chlorides, bromides and fluorides can be obtained in up to 91 percent yield and complete Z selectivity. This method can be used to easily synthesize biologically active compounds and to perform the site- and stereoselective fluorination of other organic compounds.

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          Most cited references62

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          Applications of Fluorine in Medicinal Chemistry.

          The role of fluorine in drug design and development is expanding rapidly as we learn more about the unique properties associated with this unusual element and how to deploy it with greater sophistication. The judicious introduction of fluorine into a molecule can productively influence conformation, pKa, intrinsic potency, membrane permeability, metabolic pathways, and pharmacokinetic properties. In addition, (18)F has been established as a useful positron emitting isotope for use with in vivo imaging technology that potentially has extensive application in drug discovery and development, often limited only by convenient synthetic accessibility to labeled compounds. The wide ranging applications of fluorine in drug design are providing a strong stimulus for the development of new synthetic methodologies that allow more facile access to a wide range of fluorinated compounds. In this review, we provide an update on the effects of the strategic incorporation of fluorine in drug molecules and applications in positron emission tomography.
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            Palladium-catalyzed cross-coupling: a historical contextual perspective to the 2010 Nobel Prize.

            In 2010, Richard Heck, Ei-ichi Negishi, and Akira Suzuki joined the prestigious circle of Nobel Laureate chemists for their roles in discovering and developing highly practical methodologies for C-C bond construction. From their original contributions in the early 1970s the landscape of the strategies and methods of organic synthesis irreversibly changed for the modern chemist, both in academia and in industry. In this Review, we attempt to trace the historical origin of these powerful reactions, and outline the developments from the seminal discoveries leading to their eminent position as appreciated and applied today. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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              Organic fluorine compounds: a great opportunity for enhanced materials properties.

              Interactions of "organic fluorine" have gained great interest not only in the context of crystal engineering, but also in the systematic design of functional materials. The first part of this tutorial review presents an overview on interactions known by organic fluorine. This involves π-π(F), C-F···H, F···F, C-F···π(F), C-F···π, C-F···M(+), C-F···C=O and anion-π(F) interactions, as well as other halogen bonds. The effect of the exchange of H vs. F is discussed by means of several examples and a short introduction to the young field of "fluorous" chemistry is given. The second part is dedicated to numerous applications of fluorine and fluorous interactions. It is shown how application of fluorination is used to enable a number of reactions, to improve materials properties and even open up new fields of research.
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                Author and article information

                Journal
                0410462
                6011
                Nature
                Nature
                Nature
                0028-0836
                1476-4687
                6 February 2016
                24 March 2016
                24 September 2016
                : 531
                : 7595
                : 459-465
                Affiliations
                [1 ] Department of Chemistry , Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts, 02467, USA.
                [2 ] Department of Chemistry , Massachusetts Institute of Technology , Cambridge, Massachusetts, 02139, USA.
                Author notes
                Correspondence and requests for materials should be addressed to A.H.H. ( amir.hoveyda@ 123456bc.edu ).
                Article
                NIHMS757164
                10.1038/nature17396
                4858352
                27008965
                5f88e119-eb00-407d-846a-229e9be4d603

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