2026-09-19T22:14:32Zhttps://dspace.mit.edu/server/oai/requestoai:dspace.mit.edu:1721.1/1521282023-09-14T03:30:53Zcom_1721.1_7582com_1721.1_7581col_1721.1_131022
Buchwald, Stephen L
Knippel, James Levi
Massachusetts Institute of Technology. Department of Chemistry
2023-09-13T18:07:08Z
2023-09-13T18:07:08Z
2023-06
2023-09-05T20:09:02.793Z
https://hdl.handle.net/1721.1/152128
0000-0002-3867-4372
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.
Ph.D.
Massachusetts Institute of Technology
Attribution-ShareAlike 4.0 International (CC BY-SA 4.0)
Copyright retained by author(s)
https://creativecommons.org/licenses/by-sa/4.0/
Development of Stereoselective Hydrofunctionalization Reactions Enabled by Dual Copper (I) Hydride and Palladium Catalysis
Thesis
application/pdf
Doctoral
Doctor of Philosophy
Publication
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unknown
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<Abstract>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.</Abstract>
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