Home
Resources
Publications
Synthesis of Bromo-, Boryl-, and Stannyl-Functionalized 1,2-bis(trimethylsilyl)benzenes via Diels-Alder or C-H Activation Reactions

Synthesis of Bromo-, Boryl-, and Stannyl-Functionalized 1,2-bis(trimethylsilyl)benzenes via Diels-Alder or C-H Activation Reactions

Christian Reus, Nai-Wei Liu, Michael Bolte, Hans-Wolfram Lerner, Matthias Wagner

J Org Chem. 2012 Apr 6;77(7):3518-23.

PMID: 22409628

Abstract:

1,2-Bis(trimethylsilyl)benzenes are key starting materials for the synthesis of benzyne precursors, Lewis acid catalysts, and certain luminophores. We have developed efficient, high-yield routes to functionalized 4-R-1,2-bis(trimethylsilyl)benzenes, starting from either 1,2-bis(trimethylsilyl)acetylene/5-bromopyran-2-one (2) or 1,2-bis(trimethylsilyl)benzene (1)/bis(pinacolato)diborane. In the first reaction, 5 (R = Br) is obtained through a cobalt-catalyzed Diels-Alder cycloaddition. The second reaction proceeds via iridium-mediated C-H activation and provides 8 (R = Bpin). Besides its use as a Suzuki reagent, compound 8 can be converted into 5 with CuBr(2) in i-PrOH/MeOH/H(2)O. Lithium-bromine exchange on 5, followed by the addition of Me(3)SnCl, gives 10 (R = SnMe(3)), which we have applied for Stille coupling reactions. A Pd-catalyzed C-C coupling reaction between 5 and 8 leads to the corresponding tetrasilylbiphenyl derivative. The bromo derivative 5 cleanly undergoes Suzuki reactions with electron-rich as well as electron-poor phenylboronic acids.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP17865111	4-(Trimethylsilyl)phenylboronic acid		17865-11-1	Price

As a specialist in analytical chemical Products, Alfa Chemistry offers consumers a wealth of raw materials and a full range of technologies and services.

QUICK LINKS

HEADQUARTERS

Tel:

Fax:

Email: