A diastereoselective synthesis 1-trimethylsilyl-(E)-1,3-alkenynes and a simple synthesis of alkyl trimethylsilylethynyl ketones via organoboranes |
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Authors: | Narayan G. Bhat Patricia Wawroski Gonzalo Perez-Garcia Mayra Elizondo |
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Affiliation: | Department of Chemistry, University of Texas-Pan American, 1201 West University Drive, Edinburg, TX 78541-2999, USA |
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Abstract: | A convenient, novel diastereoselective synthesis of 1-trimethylsilyl-(E)-1,3-alkenynes and a convenient synthesis of alkyl trimethylsilylethynyl ketones based on Z-1-bromo-1-alkenylboronate esters are developed. α-Bromo-(Z)-1-alkenylboronate esters readily available using literature procedures smoothly undergo a reaction with trimethylsilylethynyllithium (derived from the deprotonation of trimethylsilylethyne with n-butyllithium) in tetrahydrofuran to provide the corresponding ‘ate’ complexes. These ‘ate’ complexes undergo intramolecular nucleophilic substitution reactions to afford the corresponding (E)-1-alkenylboronate esters containing trimethylsilylethynyl moiety which upon protonolysis with acetic acid provide the corresponding 1-trimethylsilyl-(E)-1,3-alkenynes in good yields (70-82%) and in high stereochemical purities (>98%). These intermediates upon oxidation with hydrogen peroxide and sodium acetate afford the corresponding alkyl trimethylsilylethynyl ketones in good yields (66-78%). |
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Keywords: | Organoboranes Diastereoselective |
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