Rational Design of Improved Pd(II) Precatalysts And Their Application Towards New Cross-Coupling Reactions [electronic resource].

9780355027624

Ann Arbor : ProQuest Dissertations & Theses, 2017

1 online resource (227 p.)

Access is available to the Yale community.

Access restricted by licensing agreement.

This thesis summarizes the development of a family of highly active allyl-type Pd(II) precatalysts, based on an indenyl scaffold. Chapter 1 provides a review of the most recent advances in the area of Pd precatalysts that have been used to facilitate various cross-coupling reactions. Precatalysts in the +2, +1 and 0 oxidation state are all prevalent in the field. Chapter 2 details the application of previous work from the Hazari lab which determined the processes that govern the efficiency of allyl-type precatalysts. A convenient precursor, (n3-1- tBu-Indenyl) 2(micro-Cl)2Pd2, was developed that, upon addition of a ligand, forms a highly active precatalyst, (n 3-1-tBu-Indenyl)Pd(L)Cl. This precatalyst scaffold can accommodate both phosphine and N-Heterocyclic carbene (NHC) ligands, while maintaining a high degree of catalytic activity for various cross-coupling reactions. Chapter 3 offers experimental and computational insights into the mechanism of activation for allyl-type Pd(II) precatalysts and additional rationale for the superior performance of indenyl-based systems over allyl and cinnamyl. Chapters 4 and 5 discuss the development of Suzuki-Miyaura and Hiyama-Denmark couplings of aryl sulfamates using the (n 3-l-tBu-Indenyl)Pd(L)Cl scaffold; Chapter 4 focuses on the catalytic results while Chapter 5 delves deeper into these results from a computational perspective. The appendix to this thesis details related work done with a (n5-cyclopentapienyl)Pd(IPr)Cl complex and its moderate catalytic capabilities.

Books / Online / Dissertations & Theses

English

January 29, 2018

Thesis (Ph.D.)--Yale University, 2017.

Yale University.