42 research outputs found

    How Do Personal Remittances Affect Income Inequality?

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    We research the effects of personal remittances sent to a country on that country\u27s degree of income inequality. Based on data we collected for the World Bank Databank from 1970 to present we compared the effect that remittances have on the income share held by the top 20 percent of the population vs their effect on income share held by lowest 20 percent. The results from comparing the two models indicate that personal remittances decrease the spread of income leading to a decrease in the income gap of lower to middle income countries. This is due to their greater effect on the income of the lowest 20 percent over the income of the highest. Our findings are similar to those of previous studies on the effects of remittances on income

    IDPi Catalysis - The Hosomi–Sakurai Allylation and a Mukaiyama Aldol Reaction with Enolsilanes of Acetaldehyde

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    The following work describes the development and application of imidodiphosphorimidates (IDPi) in enantioselective organic Lewis acid catalysis. This new class of catalysts was generated by the replacement of the O-atoms of the BrĂžnsted acidic and Lewis basic sites of the core of previously developed imidodophosphate (IDP) catalysts by NTf groups (the "Yagupolskii principle"). IDPi are of sufficiently enhanced BrĂžnsted acidity and weakened Lewis basicity for the application in "silylium" Lewis acid catalysed transformations. Therefore, while IDP were catalytically inactive, silylated IDPi activated aldehydes for the addition of even weakly nucleophilic silanes. One long standing problem in this regard has been the enantioselective addition of allyltrimethylsilane to aldehydes, the "Hosomi-Sakurai" allylation. This transformation was beyond reach with the previously developed organic Lewis acid disulfonimide (DSI) precatalysts. By fine-tuning of the catalyst structure, a highly enantioselective allylation of a variety of aromatic and even simple aliphatic aldehydes was enabled, at catalysts loadings as low as 0.05mol%. The products obtained by this method, homoallylic alcohols, are frequently applied as intermediates for the synthesis of (protected) acetaldehyde aldols within 2 more steps, by O-protection and olefin oxidation. With our powerful new catalysts, we realized a single step enantioselective method to synthesize these aldols in a Mukaiyama aldol reaction with simple enolsilanes of acetaldehyde. Various functionalized and unfunctionalized aromatic and aliphatic aldehydes were readily transformed into the corresponding single aldolisation products in high yields and enantiomeric ratios, at short reaction times (5 min to 10 h) with low catalyst loadings (0.5-2.0 mol%). The method described in this thesis have solved long-standing problems in organic synthesis. Inexpensive, non-toxic allyltrimethylsilane can now be used for highly enantioselective allylations of aldehydes. While other strong Lewis acids such as triflimide catalyse the oligomerisation of enolsilanes of acetaldehyde, our IDPi successfully distinguishes substrate and product aldehydes, enabling highly enantioselective single step syntheses of aldols which previously were accessible in only sequences of several transformations

    Confinement-Controlled, Either syn- or anti-Selective Catalytic Asymmetric Mukaiyama Aldolizations of Propionaldehyde Enolsilanes

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    Protected aldols (i.e., true aldols derived from aldehydes) with either syn- or anti- stereochemistry are versatile intermediates in many oligopropionate syntheses. Traditional stereoselective approaches to such aldols typically require several nonstrategic operations. Here we report two highly enantioselective and diastereoselective catalytic Mukaiyama aldol reactions of the TBS- or TES- enolsilanes of propionaldehyde with aromatic aldehydes. Our reactions directly deliver valuable silyl protected propionaldehyde aldols in a catalyst controlled manner, either as syn- or anti- isomer. We have identified a privileged IDPi catalyst motif that is tailored for controlling these aldolizations with exceptional selectivities. We demonstrate how a single atom modification in the inner core of the IDPi catalyst, replacing a CF3-group with a CF2H-group, leads to a dramatic switch in enantiofacial differentiation of the aldehyde. The origin of this remarkable effect was attributed to tightening of the catalytic cavity via unconventional C-H hydrogen bonding of the CF2H group

    Total Synthesis of Sandresolide B and Amphilectolide

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    The total synthesis of the diterpenoids sandresolide B and amphilectolide from a common furan building block is presented. Key steps include palladium-mediated carbonylation, lanthanide catalyzed ring closure, Myers alkylation, intramolecular Friedel–Crafts acylation, photooxygenation, and a Kornblum–DeLaMare rearrangement
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