Methods for the asymmetric functionalization of unstrained C(sp3)–C(sp3) bonds are rare. Now, strategies are developed for the enantioselective functionalization of allylic C(sp3)–C(sp3) bonds with a palladium catalyst through either kinetic resolution or dynamic kinetic asymmetric transformation.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 digital issues and online access to articles
$119.00 per year
only $9.92 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
![](https://cdn.statically.io/img/media.springernature.com/m312/springer-static/image/art%3A10.1038%2Fs44160-024-00556-y/MediaObjects/44160_2024_556_Fig1_HTML.png)
References
Bi, X., Zhang, Q. & Gu, Z. Transition-metal-catalyzed carbon-carbon bond activation in asymmetric synthesis. Chin. J. Chem. 39, 1397–1412 (2021). A review article that summarizes advances in asymmetric C–C bond activation.
Wen, L. et al. Multiplicative enhancement of stereoenrichment by a single catalyst for deracemization of alcohols. Science 382, 458–464 (2023). This paper reports a radical route to realize the activation of unstrained asymmetric C(sp3)–C(sp3) bonds.
Nogi, K. & Yorimitsu, H. Carbon−carbon bond cleavage at allylic positions: retro-allylation and deallylation. Chem. Rev. 121, 345–364 (2021). A review article that presents advances in allylic C–C bond cleavage.
Higashida, K., Smail, V., Nagae, H., Carpentier, J.-F. & Mashima, K. Nickel-catalyzed asymmetric allylic alkylation of β‑dicarbonyl compounds via C−C bond activation of 2‑allylated cyclic 1,3-diketones. ACS Catal. 13, 2156–2161 (2023). This paper reports the formation of a stereogenic centre at a position besides the cleaved allylic C(sp3)–C(sp3) bond.
Granberg, K. L. & Bäckvall, J.-E. Isomerization of (π-allyl)palladium complexes via nucleophilic displacement by palladium(0). A common mechanism in palladium(0)-catalyzed allylic substitution. J. Am. Chem. Soc. 114, 6858–6863 (1992). This paper reports the general mechanism for enantioconvergence in Pd-catalysed allylic substitutions with racemic electrophiles.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
This is a summary of: Chen, Y.-W. et al. Intermolecular asymmetric functionalization of unstrained C(sp3)–C(sp3) bonds in allylic substitution reactions. Nat. Synth. https://doi.org/10.1038/s44160-024-00555-z (2024).
Rights and permissions
About this article
Cite this article
Asymmetric allylic C(sp3)–C(sp3) bond functionalization. Nat. Synth (2024). https://doi.org/10.1038/s44160-024-00556-y
Published:
DOI: https://doi.org/10.1038/s44160-024-00556-y