Diastereoselective Synthesis of Cyclopentenes via RhII-Catalyzed C-H Insertion Directed by a Planar Chiral N-Oxazolidinoyl Iron(0) Tricarbonyl Diene Complex
Date of Award
© 2019 Benjamin G. Hejna. All rights reserved. This work is freely available courtesy of the author. It may only be used for non-commercial, educational, and research purposes. For all other uses, including reproduction and distribution, please contact the copyright holder.
Bachelor of Arts
Chemistry & Biochemistry
Robert S. Paley
Herein is presented a general methodology for the synthesis of cyclopentenes bearing two consecutive, diastereoselectively generated stereocenters by Rhᴵᴵ-catalyzed C-H insertion using a planar chiral N-oxazolidinoyl iron(0) tricarbonyl diene complex as a steric directing group. The majority of this work is dedicated to designing and accessing viable substrates to undergo the aforementioned diastereomerically selective C-H insertion, as well as determination of the absolute stereochemical configuration of the enantiomerically pure product. We hypothesize that the observed stereochemical outcome is caused by the favorability of orienting the substituent on each newly-generated stereocenter away from the sterically bulky iron(0) tricarbonyl fragment. In addition to this methodology, a number of other methods are presented describing the reactivity of N-oxazolidinoyl iron(0) tricarbonyl dienes, including novel diazo transfers, mild removal of the oxazolidinone auxiliary, and diastereoselective intramolecular cyclizations, oxidative removal of the iron(0) tricarbonyl moiety, as well as steps towards electrochemical decomplexation.
Hejna, Benjamin G. , '19, "Diastereoselective Synthesis of Cyclopentenes via RhII-Catalyzed C-H Insertion Directed by a Planar Chiral N-Oxazolidinoyl Iron(0) Tricarbonyl Diene Complex" (2019). Senior Theses, Projects, and Awards. 238.