Dearomative reduction of arenes through the use of arenophiles & studies towards the synthesis of cardiotonic steroids calotropin and calactin

A novel method for the dearomative reduction of arenes through the use of N,N-arenophile, MTAD, was developed. Cheap feedstock arenes undergo photocycloaddition with MTAD, and the cycloadduct can be treated further to furnish novel 1,3-cyclohexadienes or 1,4-diamino-2- cyclohexenes. The utility of this method is shown in the synthesis of a natural product in two steps from naphthalene. Calotropin, a cardiotonic steroid, isolated from Apocynaceae plants is a highly cytotoxic natural product with anti-cancer activity. A total synthesis strategy which utilizes a NHC-catalyzed benzoin condensation, and Pd-catalyzed nucleophilic dearomatization of a phenol is described. Also described, is the semisynthetic strategy towards calotropin from estrone, where the aromatic A ring is dearomatized to introduce a C1 fragment at the para-position.

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

2017

Author dc:creator

• Nakamata Huynh, Stephanie Mio

Contributors dc:contributor

• Sarlah, David

• Organic chemistry
• Total synthesis
• Methodology
• Dearomative functionalization

Statement dc:rights

• Copyright 2017 Stephanie Nakamata Huynh

Language dc:language

en

Handle dc:identifier

http://hdl.handle.net/2142/97622

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/97622