Transition Metal Catalyzed Approaches to the Asymmetric Construction of All-Carbon Quaternary Centers

Citation

Moghadam, Farbod Arya (2026) Transition Metal Catalyzed Approaches to the Asymmetric Construction of All-Carbon Quaternary Centers. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/11d1-9b20. https://resolver.caltech.edu/CaltechTHESIS:06252025-233846076

Abstract

In the Stoltz group, chemical research leverages the interplay between methods development and total synthesis, wherein new synthetic technologies enable the pursuit of novel target compounds and challenges encountered during synthetic campaigns inspire the invention of methodologies. Given the stereochemical complexity of natural products and emerging pharmaceuticals, methods development in our group has focused in particular on the asymmetric construction of all-carbon quaternary centers. Herein is described the development of transition metal catalyzed approaches to the formation of such centers with high levels of stereocontrol. Chapter 1 describes the discovery of an Ir-catalyzed asymmetric allylic alkylation reaction efficiently merging linear, trisubstituted allylic electrophiles with prototypical malonate nucleophiles to generate enantioenriched β-quaternary carbonyl products. The reaction proceeds with low catalyst loadings of iridium and at ambient temperature, marking the first reaction of its kind to be performed under such mild conditions. Appendix 2 highlights recent efforts to develop an Ir-catalyzed process for the doubly stereoselective formation of vicinal quaternary stereocenters. Chapter 2 discloses a more sustainable, Mo-catalyzed alternative to the Ir-catalyzed process in Chapter 1, unveiling thus far unknown reactivity with molybdenum and generating the desired products with outstanding enantioselectivity. This advance was enabled by exhaustive investigation of suitable ligand scaffolds, ultimately leading to the creation of the novel, C1-symmetric ShabyDACH ligand. Chapter 3 discusses the elaboration of a Pd-catalyzed a-vinylation of lactam nucleophiles to forge a-quaternary carbonyls. These products could further be diversified to a range of elusive scaffolds, highlighting their synthetic utility.

Item Type:

Thesis (Dissertation (Ph.D.))

Subject Keywords:

transition metal catalysis, organic synthesis

Degree Grantor:

California Institute of Technology

Division:

Chemistry and Chemical Engineering

Major Option:

Chemistry

Thesis Availability:

Not set

Research Advisor(s):

Stoltz, Brian M.

Thesis Committee:

Nelson, Hosea M. (chair)
Demirer, Gozde S.
Peters, Jonas C.
Stoltz, Brian M.

Defense Date:

11 June 2025

Funders:

Funding Agency	Grant Number
NIH	NIHP.GM145239

Record Number:

CaltechTHESIS:06252025-233846076

Persistent URL:

https://resolver.caltech.edu/CaltechTHESIS:06252025-233846076

DOI:

10.7907/11d1-9b20

Related URLs:

URL	URL Type	Description
https://doi.org/10.1021/jacs.2c02960	DOI	Article adapted for Ch1
https://doi.org/10.26434/chemrxiv-2025-41644	DOI	Article adapted for Ch2
https://doi.org/10.1021.acs.orglett.4c02551	DOI	Article adapted for Ch3

ORCID:

Author	ORCID
Moghadam, Farbod Arya	0009-0005-4442-2349

Default Usage Policy:

No commercial reproduction, distribution, display or performance rights in this work are provided.

ID Code:

17488

Collection:

CaltechTHESIS

Deposited By:

Farbod Moghadam

Deposited On:

09 Jul 2025 19:54

Last Modified:

09 Jul 2025 19:54

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