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4.
Angew Chem Int Ed Engl ; 55(2): 639-43, 2016 Jan 11.
Artigo em Inglês | MEDLINE | ID: mdl-26610732

RESUMO

A total synthesis of the chlorosulfolipid (+)-danicalipin A has been accomplished in 12 steps and 4.4% overall yield. The efficient and scalable synthesis enabled in-depth investigations of the lipid's biological properties, in particular cytotoxicity towards various mammalian cell lines. Furthermore, the ability of (+)-danicalipin A to increase the uptake of fluorophores into bacteria and mammalian cells was demonstrated, indicating it may enhance membrane permeability. By comparing (+)-danicalipin A with racemic 1,14-docosane disulfate, and the diol precursor of (+)-danicalipin A, we have shown that both chlorine and sulfate functionalities are necessary for biological activity.


Assuntos
Lipídeos/farmacologia , Animais , Linhagem Celular , Corantes Fluorescentes/química , Células HT29 , Humanos , Lipídeos/síntese química , Camundongos
5.
J Am Chem Soc ; 134(42): 17384-7, 2012 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-23030065

RESUMO

Discrete three-coordinate borenium salts 1c and 1d are accessed by cooperative Lewis acid-base pair-mediated heterolytic splitting of the B-H bond in pinacolborane by B(C(6)F(5))(3)·DABCO and Ph(3)C(+)/DABCO, respectively. The resulting salts are competent catalysts in the reduction of a broad range of imines and can be generated in situ. Moreover, a mechanistic framework for borenium catalysis based on experimental evidence is proposed. The reaction is suggested to proceed by borenium activation of the imine substrate followed by counterintuitive hydride delivery from HBPin (with the assistance of DABCO) rather than from the HB(C(6)F(5))(3)(-) anion, contrary to typical mechanisms of reduction in FLP systems.

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