Development of Stereoselective Hydrofunctionalization Reactions Enabled by Dual Copper (I) Hydride and Palladium Catalysis

Copper(I) hydride (CuH) complexes are versatile reagents for the reduction of carbonyl compounds, Michael acceptors, and olefins. Further, the hydrocupration of unsaturated species (olefins, dienes, alkynes etc.) offers convenient access to catalytic amounts of stereodefined organometallic nucleophiles. These in situ generated organocopper species can be subsequently trapped by a variety of electrophiles for productive bond-forming reactions. This dissertation describes several new CuH-catalyzed hydrofunctionalization reactions, particularly those which rely on dual CuH- and Pd-catalysis. Chapter one offers a synopsis on the history of CuH catalysis and the seminal discoveries in dual CuH- and Pd-catalyzed reactions. Chapter two describes the CuH-catalyzed C2-allylation of benzimidazoles. Chapter three details the discovery of the dual CuH- and Pd-catalyzed hydroalkenylation of olefins. In chapter four, the development of a dual CuH- and Pd-catalyzed synthesis of Z-dienes is recounted. The final chapter covers the hydroalkenylation of vinyl metalloids, including vinyl silanes and vinyl boronate esters.

Name thesis:degree_name

Doctoral

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2023

Author dc:creator

• Knippel, James Levi

Advisor dc:contributor.advisor

• Buchwald, Stephen L

Statement dc:rights

• Attribution-ShareAlike 4.0 International (CC BY-SA 4.0)
• Copyright retained by author(s)

Licence dc:rights.uri

• https://creativecommons.org/licenses/by-sa/4.0/

Handle dc:identifier.uri

https://hdl.handle.net/1721.1/152128

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/152128