A concise protocol for -hydromagnesiation of aryl alkynes was established using 1 : 1 molar combination of sodium hydride (NaH) and magnesium iodide (MgI) without the aid of any transition metal catalysts. The resulting alkenylmagnesium intermediates could be trapped with a series of electrophiles, thus providing facile accesses to stereochemically well-defined functionalized alkenes. Mechanistic studies by experimental and theoretical approaches imply that polar hydride addition from magnesium hydride (MgH) is responsible for the process.
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http://dx.doi.org/10.1039/d0sc01773f | DOI Listing |
Angew Chem Int Ed Engl
March 2023
School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, Singapore, 637371, Singapore.
A protocol for the generation of allylmagnesium reagents from 2-aryl-1,3-dienes was developed using magnesium hydride (MgH ) that is generated in situ by solvothermal treatment of sodium hydride (NaH) and magnesium iodide (MgI ) in tetrahydrofuran (THF). Downstream functionalization of the resulting allylmagnesium reagents with carbonyl compounds or alkyl (pseudo)halides delivers branched products having an allylic quaternary carbon center, whereas that with chlorosilanes resulted in formation of linear allylsilanes in regio and stereoselective manners. Further derivatizations of the homoallylic alcohols and allylsilanes were also demonstrated.
View Article and Find Full Text PDFChem Sci
May 2020
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University 637371 Singapore
A concise protocol for -hydromagnesiation of aryl alkynes was established using 1 : 1 molar combination of sodium hydride (NaH) and magnesium iodide (MgI) without the aid of any transition metal catalysts. The resulting alkenylmagnesium intermediates could be trapped with a series of electrophiles, thus providing facile accesses to stereochemically well-defined functionalized alkenes. Mechanistic studies by experimental and theoretical approaches imply that polar hydride addition from magnesium hydride (MgH) is responsible for the process.
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