Recent Advances in Photocatalytic Decarboxylative Coupling Reactions in Medicinal Chemistry

Abstract

This review covers recent advances in decarboxylative photocatalysis applicable to the medicinal chemist. The review is not intended to be exhaustive, but instead is focussed on transformations that could be useful in the synthesis of drug-like compounds in order to highlight the utility of this methodology in the development of new pharmaceutical candidates.1 Introduction2 C–C Bond Formation3 C–N and C–O Bond Formation4 Fluorination and Trifluoromethylation5 Hydrodecarboxylation6 Protein Functionalisation7 Conclusion

Visible Light-Driven Radical-Mediated C–C Bond Cleavage/Functionalization in Organic Synthesis

“…Recently, with the rapid development of visible light photoredox catalysis, the photoredox-catalyzed radical-mediated decarboxylation of carboxylic acids and their derivatives has also been established as a potentially useful platform for C–C bond cleavage/functionalization. In this context, the research groups of MacMillan, Baran, Waser, Xiao and Lu, and others , have made many significant contributions to this field, and they have been well documented in several recent reviews − and a book chapter . In this section, we will discuss the most recent developments in the C–C bond cleavage-involved decarboxylation reactions of carboxylic acids and α-keto acids.…”

Nickel-catalyzed site- and stereoselective reductive alkylalkynylation of alkynes

“…The residue was purified by flash column chromatography through silica gel using hexane as eluent to give 12 (28 mg, 75%) as a colorless oil. Procedure for synthesis of 13 [7] : To a 4 mL vial was charged with Lindlar catalyst (0.005 mmol, 10.6 mg), 12 (0.1 mmol, 21 µL) and cyclohexane (2 mL). The reaction mixture was stirred at room temperature for 76 min under a H2 atmosphere using a balloon.…”

“…After this time, the reaction was quenched with 0. Procedure for synthesis of 17 [7] : To a 4 mL vial was charged with Lindlar catalyst (0.001 mmol, 2.1 mg), 4z (0.1 mmol, 29 mg) and cyclohexane (2 mL). The reaction mixture was stirred at room temperature for 13 h under a H2 atmosphere using a balloon.…”

Photochemical Strategy for Carbon Isotope Exchange with CO2

“…The invention of a reversible carboxylation process under mild conditions still constitutes a fundamental challenge. Inspired by pioneering works on transition-metal-free photocatalyzed carboxylation and the wealth of knowledge on the photocatalyzed radical decarboxylation of Csp 3 carboxylic acids, we report the first photocatalytic approach for CIE (Figure B). This protocol allows the insertion of the desired isotope into phenyl acetic acids, including non-natural phenyl glycine amino acids (Figure C), at 42 °C only and without the need for structural modifications or prefunctionalization.…”