The scope and limitations of 1,3-stannyl shift-promoted intramolecular cyclizations of alpha-stannyl radicals with a formyl group |
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Authors: | Ueng Shau-Hua Chen Ming-Jen Chu Shu-Fang Shao Yar-Fang Fan Gang-Ting Chang Sheng-Yueh Tsai Yeun-Min |
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Institution: | Department of Chemistry, National Taiwan University, Taipei, Taiwan 106, Republic of China. |
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Abstract: | Alpha-tributylstannyl radicals can be generated from the corresponding bromides or xanthates. These radicals undergo efficient intramolecular 1,5-cyclizations with a formyl group. The resulting beta-stannyl alkoxy radicals proceed through a 1,3-stannyl shift from carbon to oxygen to afford beta-stannyloxy radicals. This novel rearrangement is most likely irreversible and serves as a driving force to promote the cyclizations. Although the cyclization rates can be accelerated when the formyl group carries alpha-dimethyl substituents, unfortunately beta-scission of the alkoxy radicals becomes competitive with the 1,3-stannyl shift. The beta-stannyloxy radicals can be employed in further cyclizations to obtain tandem cyclization products. |
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