Explorations in Novel Photochemical Modes of Radical-Alkene Reactivity: My Piece of the π / Mark Wesley Campbell.

Format:

Book

Thesis/Dissertation

Author/Creator:

Campbell, Mark Wesley, author.

Contributor:

University of Pennsylvania. Chemistry, degree granting institution.

Language:

English

Subjects (All):

Organic chemistry.

Chemistry--Penn dissertations.

Penn dissertations--Chemistry.

Local Subjects:

Organic chemistry.

Chemistry--Penn dissertations.

Penn dissertations--Chemistry.

Physical Description:

1 online resource (422 pages)

Distribution:

Ann Arbor : ProQuest Dissertations & Theses, 2022

Contained In:

Dissertations Abstracts International 84-01B.

Place of Publication:

[Philadelphia, Pennsylvania] : University of Pennsylvania, 2022.

Language Note:

English

Summary:

The formation of Csp3-Csp3 bonds is arguably the most critical transformation in organic synthesis. For many years the Michael addition which utilizes highly reactivity organometallic carbon nucleophiles which are "poised to react" was used to achieve hydroalkylation of activated alkenes. Furthermore, this mode of reactivity also offered the potential to use other electrophiles to perform vicinal (1,2) alkene difunctionalization. Though effective in many contexts this reaction is often plagued by functional group incompatibilities, poor 1,2 vs 1,4 addition selectivity and unstable precursors. In contrast to organometallic carbanions, carbon radicals display much more selective reactivity, particularly with alkenes, and demonstrate much improved chemoselectivity. The Giese addition utilizes carbon radicals typically generated from alkyl halides via halogen atom abstraction to engage in hydroalkylation with activated alkenes. Unfortunately, the harsh conditions and reagents required for the radical chain mechanisms employed in Giese reactions restrict the transformation to alkene hydroalkylations with minimal functional group compatibility. However, several modes of photochemical catalysis can be used for radical generation which are significantly milder and more tolerance than typical radical initiation used in classical Giese addition protocols. These catalytic mechanisms offer the potential for further functionalization of radical addition intermediates opening the door a wide variety of alkene difunctionalizations with dramatically improved functional group compatibility compared to classical vicinal difunctionalizations. Herein are reported personal explorations in novel radical alkene reactions facilitated via photochemical modes of catalysis.

Notes:

Source: Dissertations Abstracts International, Volume: 84-01, Section: B.

Includes supplementary digital materials.

Advisors: Molander, Gary A.; Committee members: Kozlowski, Marisa C.; Smith, Amos B.; Winkler, Jeffrey D.

Department: Chemistry.

Ph.D. University of Pennsylvania 2022.

Local Notes:

School code: 0175

ISBN:

9798837517259

Access Restriction:

Restricted for use by site license.