1432736-89-4Relevant academic research and scientific papers
Silicon as a powerful control element in HDDA chemistry: redirection of innate cyclization preferences, functionalizable tethers, and formal bimolecular HDDA reactions
Hoye, Thomas R.,Lynn, Mandy,Pierson Smela, Merrick
, p. 13902 - 13908 (2021/11/04)
The 1,3-diyne and diynophile in hexadehydro-Diels-Alder (HDDA) reaction substrates are typically tethered by linker units that consist of C, O, N, and/or S atoms. We describe here a new class of polyynes based on silicon-containing tethers that can be disposed of and/or functionalized subsequent to the HDDA reaction. The cyclizations are efficient, and the resulting benzoxasiloles are amenable to protodesilylation, halogenation, oxygenation, and arylation reactions. The presence of the silicon atom can also override the innate mode of cyclization in some cases, an outcome attributable to a β-silyl effect on the structure of intermediate diradicals. Overall, this strategy equates formally to an otherwise unknown, bimolecular HDDA reaction and expands the versatility of this body of aryne chemistry.
Synthesis of fluoro- and perfluoroalkyl arenes via palladium-catalyzed [4 + 2] benzannulation reaction
Zatolochnaya, Olga V.,Gevorgyan, Vladimir
, p. 2562 - 2565 (2013/06/26)
An efficient entry into densely substituted fluorinated and perfluoroalkylated benzene derivatives via chemo- and regioselective Pd-catalyzed [4 + 2] cross-benzannulation is presented. The synthetic utility of these products for the synthesis of various aromatic and heteroaromatic compounds is also demonstrated. This strategy offers a viable and quite general alternative to existing fluorination and perfluoroalkylation methods for securing these valuable molecules.
