Arenophile-mediated dearomative functionalization of unactivated arenes

Two photomediated dearomative methods are reported using an “arenophile” called MTAD. Arene-arenophile cycloadducts are formed by irradiation of mixtures of unactivated arenes and MTAD at cryogenic temperatures with visible light. These cycloadducts are subsequently used as substrates in metal-catalyzed transformations. In chapter one a palladium-catalyzed dearomative syn- 1,4-diamination of unactivated arenes is presented using simple amine nucleophiles. An enantioselective variant and a number of elaborations of the resulting products are exhibited. In chapter two a concise two-step procedure to access oxepines from simple arenes is disclosed, enabled by a manganese(II)-catalyzed epoxidation of the arene-arenophile cycloadducts. Studies toward utilizing this method in concise syntheses of natural products perilloxin and fortimicin A are also reported.

Name thesis:degree_name

M.S.

Level thesis:degree_level

Thesis

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2021

Author dc:creator

• Wertjes, William Charles

Contributors dc:contributor

• Sarlah, David

• dearomatization
• arenophile
• arene
• aromatic

Statement dc:rights

• Copyright 2020 William Wertjes

Language dc:language

en

Handle dc:identifier

http://hdl.handle.net/2142/109489

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/109489