2024-03-29T15:27:03Z
https://nagoya.repo.nii.ac.jp/oai
oai:nagoya.repo.nii.ac.jp:00024074
2023-01-16T04:54:43Z
643:666:667
A practical ortho-rearrangement of silyl group of ortho-bromophenyl silyl ethers using magnesium(0)
Hasegawa, Takashi
Kishida, Hisanori
Nomura, Nobuyoshi
open access
© 2017. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
A practical synthesis of ortho-silyl-substituted phenol from ortho-bromophenyl silyl ethers without using RLi is described. Various ortho-bromophenyl silyl ethers are treated with commercially available Mg turnings, which are easy to handle in air, and transfer of the silyl group to the ortho-position occurs in good to high yields. Selective mono-magnesiation of 2,6-dibromophenyl silyl ether is observed even in the presence of excess Mg, and ortho-bromo-6-silylphenol is obtained as the predominant product. The obtained ortho-silyl-substituted phenol is formylated with (CH2O)n/MgCl2/Et3N, and then condensation with a diamine leads to a silyl-substituted salen-type ligand in a good yield. This scheme is suitable for the large scale synthesis of silyl-substituted salen-type ligands bearing imine groups.
Elsevier
2017-02-01
eng
journal article
AM
http://hdl.handle.net/2237/26286
https://nagoya.repo.nii.ac.jp/records/24074
https://doi.org/10.1016/j.tetlet.2016.12.052
0040-4039
Tetrahedron Letters
58
5
455
457
https://nagoya.repo.nii.ac.jp/record/24074/files/3_Manuscript.pdf
application/pdf
375.8 kB
2019-02-01