Palladium-Catalyzed Silylation of 2,3-Allenols with Unactivated Disilanes: Access to 2-Silyl-1,3-butadienes and α-Silyl-β-hydroxy Vinylsilanes

Guang-Li Xu; Zhong-Xia Wang

doi:10.1021/acs.orglett.1c04141

Palladium-Catalyzed Silylation of 2,3-Allenols with Unactivated Disilanes: Access to 2-Silyl-1,3-butadienes and α-Silyl-β-hydroxy Vinylsilanes

Org Lett. 2022 Jan 21;24(2):692-696. doi: 10.1021/acs.orglett.1c04141. Epub 2022 Jan 4.

Authors

Guang-Li Xu¹, Zhong-Xia Wang^{1

2}

Affiliations

¹ CAS Key Laboratory of Soft Matter Chemistry and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, PR China.
² Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, PR China.

PMID: 35057630
DOI: 10.1021/acs.orglett.1c04141

Abstract

Regioselective silylation of 2,3-allenols with disilanes was carried out under catalysis of Pd₂dba₃/P(o-MeOC₆H₄)₃. In the presence of Cs₂CO₃, the reaction achieved 2-silyl-1,3-dienes. Reaction of 1-aryl-2,3-allenols gave the products with excellent Z/E selectivity and E-isomers as the major species. Reaction of α-alkylallenols or α-alkyl-α-aryl-allenols resulted in products with moderate Z/E selectivity and E-isomers are also major. Without a base, the reaction produced α-silyl-β-hydroxyl vinylsilanes, which were converted to 2-silyl-1,3-dienes upon treatment with Cs₂CO₃.