Broadening the scope of reactivity for neutral organic electron donors

Reduction and oxidation of functional groups are some of the fundamental transformations in inorganic and organic synthesis. Compound A has been shown to be a powerful neutral organic electron donor capable of the reductive bond cleavage of various σ-bonds. Photoactivation of donor A (to A*) has been discovered to increase the reducing power of the species therefore allowing the reduction of less activated bonds and this body of work explores examples such as: carbon-nitrogen bonds of benzyl sulfonamides and aniline derivatives; carbon-oxygen bonds of benzyl ethers, esters and carbamates; carbon-carbon bonds of benzylated carbon acids; carbon-sulfur bonds of aryl methyl sulfides, oxygen-sulfur bonds of aryl and alkyl triflate esters; and nitrogen-sulfur bonds of tosylamides and activated mesylamides. A series of nitrogen-containing substrates, B-E, was investigated for their reactivity with the photoactivated donor A*. The results of these experiments were the high-yielding carbon nitrogen bond scissions, the details of which are reported herein including a mechanistic discussion and supporting evidence. Likewise, aryl methyl sulfides F and H were cleaved in good yield with the photoactivated donor A. A number of related results demonstrate the scope of the chemistry and provide insights into the mechanism of the process. Careful analysis of the reaction by-products from the above investigations has also allowed the elucidation of the structures of a number of compounds A++, J, K, L, derived from donor A under the reaction conditions. The mechanism of formation of these species and the insight offered into donor reactivity are discussed.

Name dc:type.qualificationname

phd

Level dc:type.qualificationlevel

doctoral-pg

Grantor dc:publisher.institution

University of Strathclyde

Year dc:date.issued

2014

Author dc:creator

• O'Sullivan, Steven

DOI

10.48730/hq6m-rp29

Identifier

T13835

OAI identifier oai:identifier

oai:strathclyde:3f462541v