Skip to main content
Skip to main menu

Slideshow

Cycloadditions Enabled by Chromium(III) Photoredox Catalysis

image depicts causasian woman with long brown hair, standing in front of a laboratory fume hood
Avery Smith
Graduate Student, Department of Chemistry
University of Georgia
iSTEM-2 Building, Room 1218
Organic Seminar

Photoredox catalysis has emerged as an integral fraction of modern organic methodology.[1] Since the early 2000’s there has been a renewed interest in photochemistry, with photoredox catalysis utilizing visible light becoming a rapidly expanding field. Various transition-metal complexes have been developed and proven efficient photocatalysts; however, the two most commonly employed metals in these systems are the incredibly expensive, rare-earth metals iridium and ruthenium. Previously, the Ferreira lab has indicated the promise of Cr(III)-polypyridyl complexes to perform as effective photooxidants in the presence of visible light.[2]

Our recent work describes a direct dearomative Cr(III) photocatalyzed (3+2) cycloaddition between indoles and vinyldiazo reagents.[3] The desired cycloaddition product is obtainable in high yields, with exclusive regioselectivity. This reaction is enabled by a newly developed Cr(III) photocatalyst, with the enhanced reactivity in the reaction directly attributed to a bathochromic shift in the catalyst, allowing for stronger absorption of the catalyst in the presence of visible light. The novel Cr(III) photocatalyst considerably out-performs our previously reported Cr(III) photocatalyst and has greater stability to reaction conditions than commonly used Ru(II) photocatalysts.

Illustration of red-shifted catalyst and CR(III) catlyzation

 

[1] Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C.  Chem. Rev. 2013, 113, 5322-5363.  b) Narayanam, J. M. R.; Stephenson C. R. J.  Chem. Soc. Rev. 2011, 40, 102-113.  c) Yoon, T. P.  ACS Catal. 2013, 3, 895-902.

[2] a) Stevenson, S. M.; Shores, M. P.; Ferreira, E. M.  Angew.Chem. Int. Ed. 2015, 54, 6506-6510.  b) Sarabia, F. J.; Ferreira, E. M.  Org. Lett. 2017, 19, 2865-868.  c) Sarabia, F. J.; Li, Q.; Ferreira, E. M.  Angew. Chem. Int. Ed. 2018130, 11181-11185.

[3] Gall, B. K.ǂ; Smith, A. K.ǂ; Ferreira, E. M.  Angew. Chem. Int. Ed. 2022, 61, e202212187.

 

Research Areas:

Support Us

We appreciate your financial support. Your gift is important to us and helps support critical opportunities for students and faculty alike, including lectures, travel support, and any number of educational events that augment the classroom experience. Click here to learn more about giving.

Every dollar given has a direct impact upon our students and faculty.

Got More Questions?

Undergraduate inquiries: chemreg@uga.edu 

Registration and credit transferschemreg@uga.edu

AP Credit, Section Changes, Overrides, Prerequisiteschemreg@uga.edu

Graduate inquiries: chemgrad@uga.edu

Contact Us!

Assistant to the Department Head: Donna Spotts, 706-542-1919 

Main office phone: 706-542-1919 

Fax: 706-542-9454

Head of the Department: Prof. I. Jonathan Amster