66 research outputs found

    The Quasi-Verbal Dispute Between Kripke and 'Frege-Russell'

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    Traditional descriptivism and Kripkean causalism are standardly interpreted as rival theories on a single topic. I argue that there is no such shared topic, i.e. that there is no question that they can be interpreted as giving rival answers to. The only way to make sense of the commitment to epistemic transparency that characterizes traditional descriptivism is to interpret Russell and Frege as proposing rival accounts of how to characterize a subject’s beliefs about what names refer to. My argument relies on a development of the distinction between speaker’s reference and semantic reference

    Palladium-Catalyzed (Z)-Selective Allylation of Nitroalkanes: Access to Highly Functionalized Homoallylic Scaffolds

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    Nitroalkanes undergo decarboxylative allylation in the presence of vinyl-substituted cyclic carbonates providing a wide variety of functionalized homoallylated compounds with exquisite stereocontrol. This Pd-mediated procedure features opera- tional simplicity, versatile substrate combinations and also allows for the sequential introduction of different allyl groups in the nitroalkane scaffolds with high levels of stereocontrol through the intermediacy of a (Z)-configured palladacyclic intermediate. As far as we know, the developed protocol is the first general Pd-mediated methodology towards (Z)-configured homoallylic nitroalkanes with attractive functional group diversity

    Aluminum Catalyzed formation of Functional 1,3,2- Dioxathiolane 2-Oxides from SO2: An Easy Entry towards N- Substituted Aziridines

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    Al(III) complexes derived from aminotriphenolate ligands are shown to be excellent catalysts for the formation of cyclic sulphites from a range of (functionalized) terminal and internal epoxides, and ex situ generated sulphur dioxide. The developed catalytic protocol is characterized by its operational simplicity, wide scope in epoxide reaction partners, good to excellent isolated yields and mild reaction conditions (5070oC, p(SO2) < 1 bar). The synthetic potential of these cyclic sulphites in organic synthesis is demonstrated in the preparation of N-substituted aziridines through a three-step protocol

    Domino Synthesis of -Unsaturated -Lactams via Stereo- selective Amination of -Tertiary Allylic Alcohols

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    Tertiary allylic alcohols equipped with a carboxyl group can be smoothly aminated under ambient conditions via a conceptually new and stereoselective protocol under Pd catalysis. The in situ formed (Z)-configured -amino acid cyclizes to afford an ,- unsaturated -lactam releasing water as the only by-product. This practical catalytic transformation highlights the use of a carboxyl group acting as a hydrogen donor, stereodirecting and functional group to provide a wide series of pharma-relevant building blocks. Various control reactions support the crucial role of a carboxyl group in the substrate to mediate these transformations

    Polyatomic Anion Assistance in the Assembly of [2]Pseudorotaxanes

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    We describe the use of polyatomic anions for the quantitative assembly of ion-paired complexes displaying pseudorotaxane topology. Our approach exploits the unique ion-pair recognition properties exhibited by noncovalent neutral receptors assembled through hydrogen-bonding interactions between a bis-calix[4]­pyrrole macrocycle and linear bis-amidepyridyl-<i>N</i>-oxides. The complexation of bidentate polyatomic anions that are complementary in size and shape to the receptor’s cavity, in which six NH hydrogen-bond donors converge, induces the exclusive formation of four particle-threaded assemblies

    Exploring the Building Block Potential of Readily Accessible Chiral Zn(salen) Complexes

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    The synthesis and full characterization of a series of chiral Zn(salen) complexes comprising a 1,2-diphenyl-ethane backbone is reported. The preparation method here reported simplifies the previously communicated methodology for these types of Zn complexes that utilized air-sensitive ZnEt2 (or alike) as metalating reagent. X-ray molecular structures are also reported for representative examples of this family of Zn(salen)s. A wide range of functionality is shown to be accessible via the present route, amplifying the potential use of these (Lewis acidic) Zn complexes as molecular building blocks. Examples in this work include the formation of supramolecular assemblies having built-in bifunctionality using versatile ZnN and ZnO coordination motifs as guiding tools

    Polyatomic Anion Assistance in the Assembly of [2]Pseudorotaxanes

    No full text
    We describe the use of polyatomic anions for the quantitative assembly of ion-paired complexes displaying pseudorotaxane topology. Our approach exploits the unique ion-pair recognition properties exhibited by noncovalent neutral receptors assembled through hydrogen-bonding interactions between a bis-calix[4]­pyrrole macrocycle and linear bis-amidepyridyl-<i>N</i>-oxides. The complexation of bidentate polyatomic anions that are complementary in size and shape to the receptor’s cavity, in which six NH hydrogen-bond donors converge, induces the exclusive formation of four particle-threaded assemblies

    Polyatomic Anion Assistance in the Assembly of [2]Pseudorotaxanes

    No full text
    We describe the use of polyatomic anions for the quantitative assembly of ion-paired complexes displaying pseudorotaxane topology. Our approach exploits the unique ion-pair recognition properties exhibited by noncovalent neutral receptors assembled through hydrogen-bonding interactions between a bis-calix[4]­pyrrole macrocycle and linear bis-amidepyridyl-<i>N</i>-oxides. The complexation of bidentate polyatomic anions that are complementary in size and shape to the receptor’s cavity, in which six NH hydrogen-bond donors converge, induces the exclusive formation of four particle-threaded assemblies

    Spectroscopic Properties of Zn(Salphenazine) Complexes and their Application in Small Molecule Organic Solar Cells

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    A new family of salphen based complexes, viz. Zn(salphenazine)s, has been prepared and is characterized by a larger π-surface compared to previously reported Zn(salphen) complexes. The spectroscopic properties of these Zn(salphenazine)s have been studied in detail using UV-Vis and fluorescence spectroscopy, and further investigated by computational methods. The first application of a Zn(salphenazine) complex in a small molecule organic solar cell (smOSC) is presented showing the potential of salphenazine systems in this area

    Highly Chemo-Selective Catalytic Coupling of Substituted Oxetanes and Carbon Dioxide

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    The chemo-selective coupling of oxetanes and carbon dioxide to afford functional, heterocyclic organic compounds known as six-membered cyclic carbonates remains a challenging topic. Here we describe an effective method for their synthesis relying on the use of Al-catalysis. The catalytic reactions can be carried out with excellent selectivity for the cyclic carbonate product tolerating various (functional) groups present in the 2- and 3-position(s) of the oxetane ring, and the presented methodology is the first general approach towards the formation of six-membered cyclic carbonates (6MCCs) through oxetane/CO2 coupling chemistry. Apart from a series of substituted six-membered cyclic carbonates, also the unprecedented room temperature coupling of oxetanes and CO2 is disclosed giving, depending on the structural features of the substrate, a variety of five- and six-membered heterocyclic products. A mechanistic rationale is presented for their formation and support for the intermediary presence of a carbonic acid derivative is given. The presented functional carbonates may hold great promise as building blocks in organic synthesis and the development of new, biodegradable polymers
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