Aryne cycloaddition reactions of benzodioxasilines as aryne precursors generated by catalytic reductive ortho-C-H silylation of phenols with traceless acetal directing groups

Parham Asgari; Udaya Sree Dakarapu; Hiep H Nguyen; Junha Jeon

doi:10.1016/j.tet.2016.12.002

Aryne cycloaddition reactions of benzodioxasilines as aryne precursors generated by catalytic reductive ortho-C-H silylation of phenols with traceless acetal directing groups

Tetrahedron. 2017 Jul 20;73(29):4052-4061. doi: 10.1016/j.tet.2016.12.002. Epub 2016 Dec 8.

Authors

Parham Asgari¹, Udaya Sree Dakarapu¹, Hiep H Nguyen¹, Junha Jeon¹

Affiliation

¹ Department of Chemistry and Biochemistry, University of Texas at Arlington, TX 76019, United States.

Abstract

Diversely substituted arylsilyl triflates, as aryne precursors for aryne cycloaddition reactions, were accessed from benzodioxasilines. Catalytic reductive C-H ortho-silylation of phenols with traceless acetal directing groups was exploited to prepare benzodioxasilines. Sequential addition of MeLi and then trifluoromethanesulfonic anhydride to benzodioxasilines provided arylsilyl triflates in a single pot. Notably, this approach was successfully utilized to prepare sterically hindered 1,2,3-trisubstituted arylsilyl triflates, which ultimately underwent fluoride-mediated aryne cycloaddition.

Keywords: AryneArrylsilyl triflatesBenzodioxasilinesC-H; Silyl acetals; activationCycloaddition.

Grants and funding

R15 GM116031/GM/NIGMS NIH HHS/United States