Regioselective Anti-Silyllithiation of Propargylic AlcoholsClick to copy article linkArticle link copied!
- Somnath N. KaradSomnath N. KaradDepartment of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, JapanMore by Somnath N. Karad
- Hayate SaitoHayate SaitoDepartment of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, JapanMore by Hayate Saito
- Jun Shimokawa*Jun Shimokawa*Email: [email protected]Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, JapanMore by Jun Shimokawa
- Hideki Yorimitsu*Hideki Yorimitsu*Email: [email protected]Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, JapanMore by Hideki Yorimitsu
Abstract

Among the known hydrosilylation or carbosilylation conditions of alkynes, anti-addition of the two units across the triple bond is considered rare compared to the syn counterpart. For anti-silylative vicinal difunctionalizations, transition-metal catalysts, such as ruthenium or palladium complexes, are generally required. Accordingly, silyl alkali metals have not been employed for those anti-addition transformations. Here we demonstrate that silyllithiums can add across the triple bond of a series of propargylic alkoxides regioselectively in an anti-fashion. Upon treatment with a variety of electrophiles, the trisubstituted alkenyl lithium intermediates were transformed into highly functionalized β-silyl allylic alcohols with high regiocontrol, eventually providing tri- or tetrasubstituted alkenylsilanes stereoselectively. A classic trick for anti-addition with propargylic alkoxides has transformed anti-silylative functionalizations into a robust and reliable strategy.
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This article is cited by 2 publications.
- Xueyao Mu, Shuai Peng, Fangyao Su, Shuting Yin, Yongguo Liu, Baoguo Sun, Hongyu Tian, Sen Liang. Hydromethylthiolation of alkynes via nucleophilic addition of dimethyl disulfide in DMSO. Journal of Molecular Structure 2025, 1321 , 140226. https://doi.org/10.1016/j.molstruc.2024.140226
- Tomohiko Sato, Somnath N. Karad, Jun Shimokawa, Hideki Yorimitsu. Regioselective anti-Silyllithiation of Propargylic Amines. Synlett 2024, 35
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, 419-422. https://doi.org/10.1055/a-2047-8456
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