Photochemical Deracemization of 3‐Substituted Oxindoles

Großkopf, Johannes; Heidecker, Alexandra A.; Bach, Thorsten

doi:10.1002/ange.202305274

Cited by 1 publication

(1 citation statement)

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“…Visible (solar) light, as a sustainable energy source, can supply the necessary external perturbation to drive the deracemization reaction forward. Therefore, photochemical deracemization mediated by visible light has gained attention from the chemistry community, and some breakthroughs have been achieved recently. − Bach and co-workers reported visible-light-driven deracemization of amide-containing allenes mediated by the hydrogen bonding between chiral photosensitizer and substrates (Figure b) . The different overall sensitization rates of two enantiomers are responsible for this deracemization.…”

Section: Introductionmentioning

confidence: 99%

Photoexcited Palladium-Catalyzed Deracemization of Allenes

Song,

Bai,

et al. 2024

J. Am. Chem. Soc.

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The different enantiomers of specific chiral molecules frequently exhibit disparate biological, physiological, or pharmacological properties. Therefore, the efficient synthesis of single enantiomers is of particular importance not only to the pharmaceutical sector but also to other industrial sectors, such as agrochemical and fine chemical industries. Deracemization, a process during which a racemic mixture is converted into a nonracemic product with 100% atom economy and theoretical yield, is the most straightforward method to access enantioenriched molecules but a challenging task due to a decrease in entropy and microscopic reversibility. Axially chiral allenes bear a distinctive structure of two orthogonal cumulative π-systems and are acknowledged as synthetically versatile synthons in organic synthesis. The selective creation of axially chiral allenes with high optical purity under mild reaction conditions has always been a very popular and hot topic in organic synthesis but remains challenging. Herein, a photoexcited palladium-catalyzed deracemization of nonprefunctionalized disubstituted allenes is disclosed. This method provides an efficient and economical strategy to accommodate a broad scope of allenes with good enantioselectivities and yields (53 examples, up to 96% yield and 95% ee). The use of a suitable chiral palladium complex with visible light irradiation is an essential factor in achieving this transformation. A metal-to-ligand charge transfer mechanism was proposed based on control experiments and density functional theory calculations. Quantum mechanical studies implicate dual modes of asymmetric induction behind our new protocol: (1) sterically controlled stereoselective binding of one allene enantiomer under the ground-state and (2) facile, noncovalent interaction-driven excited-state isomerization toward the opposite enantiomer. The success of this newly established photochemical deracemization strategy should provide inspiration for expansion to other multisubstituted allenes and will open up a new mode for enantioselective excited-state palladium catalysis.

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