56-29-1Relevant articles and documents
Late-Stage Intermolecular Allylic C-H Amination
Clark, Joseph R.,Dixon, Charlie F.,Feng, Kaibo,Han, Wei,Ide, Takafumi,Koch, Vanessa,Teng, Dawei,Wendell, Chloe I.,White, M. Christina
supporting information, p. 14969 - 14975 (2021/10/01)
Allylic amination enables late-stage functionalization of natural products where allylic C-H bonds are abundant and introduction of nitrogen may alter biological profiles. Despite advances, intermolecular allylic amination remains a challenging problem due to reactivity and selectivity issues that often mandate excess substrate, furnish product mixtures, and render important classes of olefins (for example, functionalized cyclic) not viable substrates. Here we report that a sustainable manganese perchlorophthalocyanine catalyst, [MnIII(ClPc)], achieves selective, preparative intermolecular allylic C-H amination of 32 cyclic and linear compounds, including ones housing basic amines and competing sites for allylic, ethereal, and benzylic amination. Mechanistic studies support that the high selectivity of [MnIII(ClPc)] may be attributed to its electrophilic, bulky nature and stepwise amination mechanism. Late-stage amination is demonstrated on five distinct classes of natural products, generally with >20:1 site-, regio-, and diastereoselectivity.
Process for hydroformylation of olefinic compounds
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, (2008/06/13)
A hydroformylation process for unsaturated compounds such as monoolefins and diolefins is carried out in an ionic medium in which the catalytic species is dissolved, but in which the reaction products (aldehydes) formed are only slightly soluble or are insoluble. The ionic medium is liquid at a temperature below 90° C. and comprises at least one quaternary ammonium and/or phosphonium cation and at least one anion which is preferably selected from the group formed by tetrafluoroborate when the cation is ammonium, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, perfluoroalkylsulphonates, fluorosulphonate, bis-perfluoroalkylsulphonyl amides or dichlorocuprate, tetrachlorocuprate, tetrachloroaluminate, or trichlorozincate. At the end of the reaction, the organic phase is separated out and the polar phase containing the catalyst is used again.
