Presentation Title

Evaluation of a Hypervalent Iodine-Mediated Oxidative Rearrangement of Phenols

Faculty Mentor

Dr. Raul Navarro

Start Date

23-11-2019 10:00 AM

End Date

23-11-2019 10:45 AM

Location

251

Session

poster 3

Type of Presentation

Poster

Subject Area

physical_mathematical_sciences

Abstract

Hypervalent iodine-mediated oxidative phenol rearrangements are a class of reactions that yield valuable structural motifs that are stereochemically rich and biologically active; because of this, they are of great interest to synthetic chemists. The rearrangement we are pursuing would yield a highly functionalized cyclohexadienone containing a quaternary chiral center. Both motifs present a multitude of options in terms of successive reactions that can be performed, and chiral quaternary centers are a present in many biologically active natural products; being able to access it expedite research into such compounds.

Thus far, we have synthesized a viable diol substrate and are conducting experiments to determine parameters for the oxidative rearrangement; we will also test to see how the reaction of interest tolerates different structural modifications to our precursor molecule, particularly in regards to what variations of R groups are able to undergo the transposition rearrangement.

Our efforts are currently focused on the hypervalent iodine-mediated oxidation and carbocation 1,2 rearrangement in order to achieve the desired cyclohexadienone structure. Additionally, we hope to combine this dearomatization reaction with a Wagner-Meerwein transposition rearrangement; reactivity similar to what we hope to promote was documented by Gue´rard et al. in 2009. The alkyl shift that this reaction should induce would yield the quaternary chiral structure discussed above.

The immediate focus of our research will be determining the optimal solvent in the Wagner-Meerwein rearrangement. Solvents currently being considered are hexafluoro isopropanol, trifluoro isopropanol, dichloromethane, and acetonitrile; the reason behind this is to compare the effectiveness of highly ionizing solvents against less polar solvents. Once we have established reaction parameters for the Wagner-Meerwein, we will begin determining how the rearrangement tolerates variations in the base structure of the molecule establishing the range of R groups that can be used.

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Nov 23rd, 10:00 AM Nov 23rd, 10:45 AM

Evaluation of a Hypervalent Iodine-Mediated Oxidative Rearrangement of Phenols

251

Hypervalent iodine-mediated oxidative phenol rearrangements are a class of reactions that yield valuable structural motifs that are stereochemically rich and biologically active; because of this, they are of great interest to synthetic chemists. The rearrangement we are pursuing would yield a highly functionalized cyclohexadienone containing a quaternary chiral center. Both motifs present a multitude of options in terms of successive reactions that can be performed, and chiral quaternary centers are a present in many biologically active natural products; being able to access it expedite research into such compounds.

Thus far, we have synthesized a viable diol substrate and are conducting experiments to determine parameters for the oxidative rearrangement; we will also test to see how the reaction of interest tolerates different structural modifications to our precursor molecule, particularly in regards to what variations of R groups are able to undergo the transposition rearrangement.

Our efforts are currently focused on the hypervalent iodine-mediated oxidation and carbocation 1,2 rearrangement in order to achieve the desired cyclohexadienone structure. Additionally, we hope to combine this dearomatization reaction with a Wagner-Meerwein transposition rearrangement; reactivity similar to what we hope to promote was documented by Gue´rard et al. in 2009. The alkyl shift that this reaction should induce would yield the quaternary chiral structure discussed above.

The immediate focus of our research will be determining the optimal solvent in the Wagner-Meerwein rearrangement. Solvents currently being considered are hexafluoro isopropanol, trifluoro isopropanol, dichloromethane, and acetonitrile; the reason behind this is to compare the effectiveness of highly ionizing solvents against less polar solvents. Once we have established reaction parameters for the Wagner-Meerwein, we will begin determining how the rearrangement tolerates variations in the base structure of the molecule establishing the range of R groups that can be used.