Designing a Library of Conjugated Planar Chiral Rh(III) Indenyl Catalysts and Progress Towards an Enantioselective Intramolecular 1,2-Arylamination of Terminal Olefins using Planar Chiral Rh(III) Indenyl Catalysts Restricted; Files Only

Abstract

In recent years, planar chiral transition-metal indenyl complexes have emerged as powerful catalysts in various organic transformations, garnering significant attention among researchers. Rhodium catalysis, in particular, has received much attention due to its unique reactivity and selectivity in asymmetric reactions, notably in C-H functionalization. Following the success of the initial generation of a planar chiral Rh(III) indenyl catalyst for regio- and enantioselective allylic C-H amidation, there is a concerted effort build a library of these catalysts to leverage the indenyl effect for stereoselectivity. Herein, we report a modular synthetic strategy to access four highly conjugated indenyl ligands for future studies on the Rh(III) indenyl complexes. Additionally, we report exciting progress towards a novel method for the regio- and enantioselective synthesis of 2-aminotetralins from the readily available starting material 3-butenylbenzene. With the assistance of my graduate mentor Patrick Gross, we believe this method will not only be beneficial for the synthesis of pharmaceutically relevant compounds containing the 2-aminotetralin core but also introduce another nitrogenous compound that can be synthesized by our planar chiral Rh(III) indenyl catalyst, thus highlighting its potential as a highly privileged chiral catalyst in organic synthesis.

Table of Contents

CHAPTER 1 SYNTHESIS OF CONJUGATED LIGANDS FOR PLANAR CHIRAL INDENYL RH(III) CATALYSTS

1.1 Overview of Cyclopentadienyl and Indenyl Transition-Metal Catalysis

1.2 Results and Discussion

1.3 Conclusion and Future Direction

CHAPTER 2 PROGRESS TOWARDS A REGIO- AND ENANTIOSELECTIVE 1,2-ARYL AMINATION TO ACCESS 2-AMINOTETRALINS FROM TERMINAL OLEFINS USING PLANAR CHIRAL INDENYL RH(III) CATALYSTS

2.1 Overview of 2-Aminotetralins and its Synthesis

2.2 Results and Discussion

2.5 Future Directions

CHAPTER 3 CONCLUSION: WORKING TOWARDS PRIVILEGED CHIRAL CATALYSTS

REFERENCES

SUPPLEMENTAL INFORMATION

I.     General Information

II.    Synthesis of Conjugated Indenyl Ligands

III.      Preparation of Olefin Starting Materials

IV.       Synthesis of Nitrogen Source

V.    Synthesis of 2-Aminotetralins Products

VI.      Supplemental References

VII.    Spectroscopic Data

About this Honors Thesis

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School	Emory College
Department	Chemistry
Degree	B.S.
Submission	Honors Thesis
Language	English
Research Field	Chemistry, Organic
Stichwort	Rhodium Indenyl Catalyst 1,2-arylamination Planar Chiral Rh(III) Indenyl Catalysts Conjugated Planar Chiral Rh(III) Indenyl Catalysts 2-aminotetralins
Committee Chair / Thesis Advisor	Blakey, Simon, Emory University
Committee Members	Weinschenk, Matthew, Emory University Himes, Richard, Emory University

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