Merging NiH Catalysis and Inner-Sphere Metal-Nitrenoid Transfer for Hydroamidation of Alkynes
- PMID: 33834777
- DOI: 10.1021/jacs.1c01138
Merging NiH Catalysis and Inner-Sphere Metal-Nitrenoid Transfer for Hydroamidation of Alkynes
Abstract
The formal hydroamination/hydroamidation utilizing metal hydride is an appealing synthetic tool for the construction of valuable nitrogen-containing compounds from unsaturated hydrocarbons. While significant advances have been made for the functionalizations of alkenes in this realm, the direct hydroamidation of alkynes remains rather limited due to the high feasibility of the key metal-alkenyl intermediate to choose other reaction pathways. Herein, we report a NiH-catalyzed strategy for the hydroamidation of alkynes with dioxazolones, which allows convenient access to synthetically useful secondary enamides in (E)-anti-Markovnikov or Markovnikov selectivity. The reaction is viable for both terminal and internal alkynes and is also tolerant with a range of subtle functional groups. With H2O found as an essential component for high catalyst turnovers, the involvement of inner-sphere nitrenoid transfer is proposed that outcompetes an undesired semireduction process, thus representing the first example to show the competence of Ni catalysis for metal-nitrenoid formation from dioxazolones.
Similar articles
-
NiH-catalyzed C-N bond formation: insights and advancements in hydroamination of unsaturated hydrocarbons.Chem Sci. 2023 Dec 6;15(2):442-457. doi: 10.1039/d3sc05589b. eCollection 2024 Jan 3. Chem Sci. 2023. PMID: 38179526 Free PMC article. Review.
-
Anti-Markovnikov Intermolecular Hydroamination of Alkenes and Alkynes: A Mechanistic View.Chem Rev. 2023 Aug 9;123(15):9139-9203. doi: 10.1021/acs.chemrev.2c00482. Epub 2023 Jul 5. Chem Rev. 2023. PMID: 37406078 Free PMC article. Review.
-
Rhodium(III)-Catalyzed Anti-Markovnikov Hydroamidation of Unactivated Alkenes Using Dioxazolones as Amidating Reagents.J Am Chem Soc. 2022 Dec 14;144(49):22426-22432. doi: 10.1021/jacs.2c10552. Epub 2022 Dec 1. J Am Chem Soc. 2022. PMID: 36453859 Free PMC article.
-
Endo-Selective Intramolecular Alkyne Hydroamidation Enabled by NiH Catalysis Incorporating Alkenylnickel Isomerization.J Am Chem Soc. 2022 Jun 8;144(22):10064-10074. doi: 10.1021/jacs.2c03777. Epub 2022 May 27. J Am Chem Soc. 2022. PMID: 35621341
-
Mechanism-Guided Development of Transition-Metal-Catalyzed C-N Bond-Forming Reactions Using Dioxazolones as the Versatile Amidating Source.Acc Chem Res. 2021 Jun 1;54(11):2683-2700. doi: 10.1021/acs.accounts.1c00198. Epub 2021 May 12. Acc Chem Res. 2021. PMID: 33979133
Cited by
-
NiH-catalyzed C-N bond formation: insights and advancements in hydroamination of unsaturated hydrocarbons.Chem Sci. 2023 Dec 6;15(2):442-457. doi: 10.1039/d3sc05589b. eCollection 2024 Jan 3. Chem Sci. 2023. PMID: 38179526 Free PMC article. Review.
-
Rh(III)-catalyzed Intra- and Intermolecular 3,4-Difunctionalization of 1,3-Dienes via Rh(III)-π-allyl Amidation with 1,4,2-Dioxazolones.ACS Catal. 2022 Aug 5;12(15):9690-9697. doi: 10.1021/acscatal.2c02537. Epub 2022 Jul 26. ACS Catal. 2022. PMID: 37829170 Free PMC article.
-
Development of a Nickel-Catalyzed N-N Coupling for the Synthesis of Hydrazides.J Am Chem Soc. 2023 Jul 19;145(28):15071-15077. doi: 10.1021/jacs.3c04834. Epub 2023 Jul 6. J Am Chem Soc. 2023. PMID: 37413695 Free PMC article.
-
NiH-catalyzed anti-Markovnikov hydroamidation of unactivated alkenes with 1,4,2-dioxazol-5-ones for the direct synthesis of N-alkyl amides.Commun Chem. 2022 Dec 22;5(1):176. doi: 10.1038/s42004-022-00791-4. Commun Chem. 2022. PMID: 36697972 Free PMC article.
-
Silylium ion migration dominated hydroamidation of siloxy-alkynes.Commun Chem. 2022 Oct 22;5(1):133. doi: 10.1038/s42004-022-00751-y. Commun Chem. 2022. PMID: 36697660 Free PMC article.
Publication types
LinkOut - more resources
Full Text Sources
Other Literature Sources