A series of triarylolefins bearing the combretastatin A-4 and the isocombretastatin A-4 cores were synthesized and evaluated. The cooperative ortho-effect of a labile bromine atom in the regioselective hydrostannation of unsymmetrical diarylalkynes leading to stereodefined triarylolefins is presented.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1016/j.ejmech.2010.05.007 | DOI Listing |
Chemistry
December 2021
Max-Planck-Institut für Kohlenforschung, 45470, Mülheim an der RuhrMülheim/Ruhr, Germany.
Alkynyl-B(aam) (aam=anthranilamidato) derivatives are readily available bench-stable compounds that undergo remarkably selective reactions with Bu SnH in the presence of [Cp*RuCl] as the catalyst. The addition follows a stereochemically unorthodox trans-selective course; in terms of regioselectivity, the Bu Sn- unit is delivered with high fidelity to the C-atom of the triple bond adjacent to the boracyclic head group ("alpha,trans-addition"). This outcome is deemed to reflect a hydrogen bonding interaction between the protic -NH groups of the benzo-1,3,2-diazaborininone ring system and the polarized [Ru-Cl] bond in the loaded catalyst, which locks the substrate in place in a favorable orientation relative to the incoming reagent.
View Article and Find Full Text PDFJ Am Chem Soc
January 2021
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
We report an iron system, Cp*Fe(1,2-RPCHX), which controls the Markovnikov and anti-Markovnikov hydrostannation of alkynes by tuning the ionic metal-heteroatom bonds (Fe-X) reactivity. The sequential addition of BuSnH to the iron-amido catalyst (, X = HN, R = Ph) affords a distannyl Fe(IV)-H species responsible for syn-addition of the Sn-H bond across the C≡C bond to produce branched α-vinylstannanes. Activation of the C(sp)-H bond of alkynes by an iron-aryloxide catalyst (, X = O, R = Cy) affords an iron(II) vinylidene intermediate, allowing for gem-addition of the Sn-H to the terminal-carbon producing β-vinylstannanes.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
June 2018
Department of Chemistry and Biochemistry, Section of Synthesis, Materials and Chemical Biology, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA, 92093, USA.
The regioselective formation of (E)-β-vinylstannanes has been a long-standing challenge in transition-metal-catalyzed alkyne hydrostannation. Herein, we report a well-defined molybdenum-based system featuring two encumbering m-terphenyl isocyanides that reliably and efficiently delivers (E)-β-vinylstannanes from a range of terminal and internal alkynes with high regioselectivity. The system is particularly effective for aryl alkynes and can discriminate between alkyl chains of low steric hindrance in unsymmetrically substituted dialkyl alkynes.
View Article and Find Full Text PDFJ Org Chem
March 2018
Department of Chemistry and ‡Institute of Chemical Biology and Drug Discovery, Stony Brook University - State University of New York, Stony Brook, New York 11794-3400, United States.
Next-generation taxoids, such as SB-T-1214, are highly potent cytotoxic agents that exhibit remarkable efficacy against drug-resistant tumors in vivo, including those that overexpress the P-glycoprotein (Pgp) efflux pump. As SB-T-1214 is not a substrate for Pgp-mediated efflux, it may exhibit a markedly different biodistribution and tumor-accumulation profile than paclitaxel or docetaxel, which are both Pgp substrates. To investigate the biodistribution and tumor-accumulation levels of SB-T-1214 using positron emission tomography (PET), a new synthetic route has been developed to allow the incorporation of C, a commonly employed positron-emitting radionucleide, via methyl iodide at the last step of chemical synthesis.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
April 2014
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany).
In contrast to all other transition-metal-catalyzed hydrostannation reactions documented in the literature, the addition of Bu3SnH across various types of alkynes proceeds with excellent trans selectivity, provided the reaction is catalyzed by [Cp*Ru]-based complexes. This method is distinguished by a broad substrate scope and a remarkable compatibility with functional groups, including various substituents that would neither survive under the conditions of established Lewis acid mediated trans hydrostannations nor withstand free-radical reactions. In case of unsymmetrical alkynes, a cooperative effect between the proper catalyst and protic functionality in the substrate allows outstanding levels of regioselectivity to be secured as well.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!