Application of Organic Photoredox Catalysis in New Reaction Methodology: Synthesis of Butyrolactones via Polar Radical Crossover Cycloaddition and Hydrodecarboxylation of Carboxylic Acids

Public Deposited

Analytics

Last Modified

Creator

Zeller, Mary
- Affiliation: College of Arts and Sciences, Department of Chemistry

Abstract

Synthesis of Butyrolactones via Polar Radical Crossover Cycloaddition A direct catalytic synthesis of γ-butyrolactones from simple alkene and unsaturated acid starting materials is reported. The catalytic system consists of the Fukuzumi acridinium photooxidant and substoichiometric quantities of a redox-active cocatalyst. Oxidizable alkenes such as styrenes and trisubstituted aliphatic alkenes are cyclized with unsaturated acids via polar radical crossover cycloaddition (PRCC) reactions. This method has been applied to the diastereoselective total synthesis of methylenolactocin and protolichesterinic acid. Hydrodecarboxylation of Carboxylic and Malonic Acid Derivatives A direct catalytic hydrodecarboxylation of primary, secondary, and tertiary carboxylic acids is reported. The catalytic system consists of a Fukuzumi acridinium photooxidant with phenyldisulfide acting as a redox-active cocatalyst. Substoichiometric quantities of Hünig’s base are used to reveal the carboxylate. Use of trifluoroethanol as a solvent allowed for significant improvements in substrate compatibilities, as the method reported is not limited to carboxylic acids bearing α-heteroatom or –phenyl substitution. This method has been applied to the direct double decarboxylation of malonic acid derivatives, which allows for the convenient use of dimethyl malonate as a methylene synthon.

Date of publication

Keyword

DOI

Resource type

Rights statement

Advisor

Degree

Degree granting institution

Graduation year

Language

Relations

Thumbnail	Title	Date Uploaded	Visibility	Actions
	Zeller_unc_0153D_16439.pdf	2019-04-12	Public	Download