![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
Atroposelective Palladium-Catalyzed γ-C-H Olefination of BODIPYs
Youqing Yang1,2, Ping Wang1, Chenglong Yuan1
1Key Laboratory of Green and Precise Synthetic Chemistry and Applications, School of Chemistry and Chemical Engineering, Anhui Key Laboratory of Synthetic Chemistry and Applications, Ministry of Education, Huaibei Normal University, Huaibei, 235000, China.
Abstract:
Enantioenriched BODIPYs have emerged as a class of exceptionally valuable fluorophores, distinguished by their remarkable chiroptical properties and versatile applications in bioimaging, molecular sensing, and optoelectronic materials. The development of asymmetric catalytic methodologies for their synthesis represents a significant advancement in this field. Herein, we present a robust and efficient strategy for the Pd(II)-catalyzed atroposelective C-H olefination and desymmetrization at the γ-position of BODIPYs, facilitated by a thioether directing group and a chiral amino acid-derived ligand. This oxidative Heck-type reaction enables the direct synthesis of a wide array of axially chiral BODIPY derivatives with exceptional E-selectivity and outstanding enantioselectivities. The resultant chiral fluorophores exhibit tunable photophysical properties, including near-infrared emission and robust circularly polarized luminescence, and demonstrate excellent biocompatibility in live-cell imaging. This method establishes a comprehensive platform for the streamlined synthesis of axially chiral BODIPYs, thereby advancing their potential applications in cutting-edge photonic, biological, and optoelectronic technologies.
More Related Videos
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
Related Concept Videos
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
02:36Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
00:51Base-Promoted α-Halogenation of Aldehydes and Ketones
02:35Regioselectivity of Electrophilic Additions-Peroxide Effect