Development of a Nickel-Catalyzed N-N Coupling for the Synthesis of Hydrazides

doi:10.1021/jacs.3c04834

. 2023 Jul 19;145(28):15071-15077.

doi: 10.1021/jacs.3c04834. Epub 2023 Jul 6.

Development of a Nickel-Catalyzed N-N Coupling for the Synthesis of Hydrazides

Jay P Barbor¹, Vaishnavi N Nair¹, Kimberly R Sharp¹, Trevor D Lohrey¹, Sara E Dibrell¹, Tejas K Shah², Martin J Walsh², Sarah E Reisman¹, Brian M Stoltz¹

Affiliations

¹ The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
² Corteva Agriscience, 9330 Zionsville Road, Indianapolis, Indiana 46268, United States.

PMID: 37413695
PMCID: PMC10360072
DOI: 10.1021/jacs.3c04834

Development of a Nickel-Catalyzed N-N Coupling for the Synthesis of Hydrazides

Jay P Barbor et al. J Am Chem Soc. 2023.

. 2023 Jul 19;145(28):15071-15077.

doi: 10.1021/jacs.3c04834. Epub 2023 Jul 6.

Authors

Jay P Barbor¹, Vaishnavi N Nair¹, Kimberly R Sharp¹, Trevor D Lohrey¹, Sara E Dibrell¹, Tejas K Shah², Martin J Walsh², Sarah E Reisman¹, Brian M Stoltz¹

Affiliations

¹ The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
² Corteva Agriscience, 9330 Zionsville Road, Indianapolis, Indiana 46268, United States.

PMID: 37413695
PMCID: PMC10360072
DOI: 10.1021/jacs.3c04834

Abstract

A nickel-catalyzed N-N cross-coupling for the synthesis of hydrazides is reported. O-Benzoylated hydroxamates were efficiently coupled with a broad range of aryl and aliphatic amines via nickel catalysis to form hydrazides in an up to 81% yield. Experimental evidence implicates the intermediacy of electrophilic Ni-stabilized acyl nitrenoids and the formation of a Ni(I) catalyst via silane-mediated reduction. This report constitutes the first example of an intermolecular N-N coupling compatible with secondary aliphatic amines.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing financial interest.

Figures

**Figure 1**
Compounds featuring N–N bonds and nitrene-mediated synthetic strategies.

**Scheme 1. Substrate Scope**
Reactions performed on 0.2 mmol scale. Protected as TBS ether for isolation. 72 h. Silylamine (8b) used. 48 h.

**Scheme 2. Large Scale Reactions**
Reactions performed on 2 mmol scale.

**Scheme 3. Ni(I) Catalyst**
Reactions performed on 0.05 mmol scale.

See this image and copyright information in PMC

Cited by

Metal free cross-dehydrogenative N-N coupling of primary amides with Lewis basic amines.
Kathiravan S, Dhillon P, Zhang T, Nicholls IA. Kathiravan S, et al. Nat Commun. 2024 Mar 26;15(1):2643. doi: 10.1038/s41467-024-46890-9. Nat Commun. 2024. Retraction in: Nat Commun. 2024 Jun 18;15(1):5189. doi: 10.1038/s41467-024-49357-z. PMID: 38531886 Free PMC article. Retracted.

References

1. For a general overview of N–N bonds in nature, see:
2. Blair L. M.; Sperry J. Natural Products Containing a Nitrogen–Nitrogen Bond. J. Nat. Prod. 2013, 76, 794–812. 10.1021/np400124n. - DOI - PubMed
3. Chen L.; Deng Z.; Zhao C. Nitrogen–Nitrogen Bond Formation Reactions Involved in Natural Product Biosynthesis. ACS Chem. Biol. 2021, 16, 559–570. 10.1021/acschembio.1c00052. - DOI - PubMed
4. He H.-Y.; Niikura H.; Du Y.-L.; Ryan K. S. Synthetic and Biosynthetic Routes to Nitrogen–Nitrogen Bonds. Chem. Soc. Rev. 2022, 51, 2991–3046. 10.1039/C7CS00458C. - DOI - PubMed
5. Narang R.; Narasimhan B.; Sharma S. A Review on Biological Activities and Chemical Synthesis of Hydrazide Derivatives. Curr. Med. Chem. 2012, 19, 569–612. 10.2174/092986712798918789. - DOI - PubMed
1. For a general review of convergent N–N coupling, see:
2. Guo Q.; Lu Z. Recent Advances in Nitrogen–Nitrogen Bond Formation. Synthesis 2017, 49, 3835–3847. 10.1055/s-0036-1588512. - DOI
3. Tabey A.; Vemuri P. Y.; Patureau F. W. Cross-Dehydrogenative N–N Couplings. Chem. Sci. 2021, 12, 14343–14352. 10.1039/D1SC03851F. - DOI - PMC - PubMed
1. Pereira M. M.; Alcântara A. F.; de C.; Piló-Veloso D.; Raslan D. S. NMR Structural Analysis of Braznitidumine: A New Indole Alkaloid with 1,2,9-Triazabicyclo[7.2.1] System, Isolated from Aspidosperma Nitidum (Apocynaceae). J. Braz. Chem. Soc. 2006, 17, 1274–1280. 10.1590/S0103-50532006000700012. - DOI
1. Ahmed F. S.; Helmy Y. S.; Helmy W. S. Toxicity and Biochemical Impact of Methoxyfenozide/Spinetoram Mixture on Susceptible and Methoxyfenozide-Selected Strains of Spodoptera Littoralis (Lepidoptera: Noctuidae). Sci. Rep. 2022, 12, 6974–6983. 10.1038/s41598-022-10812-w. - DOI - PMC - PubMed
1. Bentué-Ferrer D.; Arvieux C.; Tribut O.; Ruffault A.; Bellissant E. Clinical Pharmacology, Efficacy and Safety of Atazanavir: A Review. Expert Opin. Drug Metab. Toxicol. 2009, 5, 1455–1468. 10.1517/17425250903321514. - DOI - PubMed

Grants and funding

LinkOut - more resources

Full Text Sources

[1] For a general overview of N–N bonds in nature, see:

Blair L. M.; Sperry J. Natural Products Containing a Nitrogen–Nitrogen Bond. J. Nat. Prod. 2013, 76, 794–812. 10.1021/np400124n. - DOI - PubMed

Chen L.; Deng Z.; Zhao C. Nitrogen–Nitrogen Bond Formation Reactions Involved in Natural Product Biosynthesis. ACS Chem. Biol. 2021, 16, 559–570. 10.1021/acschembio.1c00052. - DOI - PubMed

He H.-Y.; Niikura H.; Du Y.-L.; Ryan K. S. Synthetic and Biosynthetic Routes to Nitrogen–Nitrogen Bonds. Chem. Soc. Rev. 2022, 51, 2991–3046. 10.1039/C7CS00458C. - DOI - PubMed

Narang R.; Narasimhan B.; Sharma S. A Review on Biological Activities and Chemical Synthesis of Hydrazide Derivatives. Curr. Med. Chem. 2012, 19, 569–612. 10.2174/092986712798918789. - DOI - PubMed

[2] For a general overview of N–N bonds in nature, see:

[3] Blair L. M.; Sperry J. Natural Products Containing a Nitrogen–Nitrogen Bond. J. Nat. Prod. 2013, 76, 794–812. 10.1021/np400124n. - DOI - PubMed

[4] Chen L.; Deng Z.; Zhao C. Nitrogen–Nitrogen Bond Formation Reactions Involved in Natural Product Biosynthesis. ACS Chem. Biol. 2021, 16, 559–570. 10.1021/acschembio.1c00052. - DOI - PubMed

[5] He H.-Y.; Niikura H.; Du Y.-L.; Ryan K. S. Synthetic and Biosynthetic Routes to Nitrogen–Nitrogen Bonds. Chem. Soc. Rev. 2022, 51, 2991–3046. 10.1039/C7CS00458C. - DOI - PubMed

[6] Narang R.; Narasimhan B.; Sharma S. A Review on Biological Activities and Chemical Synthesis of Hydrazide Derivatives. Curr. Med. Chem. 2012, 19, 569–612. 10.2174/092986712798918789. - DOI - PubMed

[7] For a general review of convergent N–N coupling, see:

Guo Q.; Lu Z. Recent Advances in Nitrogen–Nitrogen Bond Formation. Synthesis 2017, 49, 3835–3847. 10.1055/s-0036-1588512. - DOI

Tabey A.; Vemuri P. Y.; Patureau F. W. Cross-Dehydrogenative N–N Couplings. Chem. Sci. 2021, 12, 14343–14352. 10.1039/D1SC03851F. - DOI - PMC - PubMed

[8] For a general review of convergent N–N coupling, see:

[9] Guo Q.; Lu Z. Recent Advances in Nitrogen–Nitrogen Bond Formation. Synthesis 2017, 49, 3835–3847. 10.1055/s-0036-1588512. - DOI

[10] Tabey A.; Vemuri P. Y.; Patureau F. W. Cross-Dehydrogenative N–N Couplings. Chem. Sci. 2021, 12, 14343–14352. 10.1039/D1SC03851F. - DOI - PMC - PubMed

[11] Pereira M. M.; Alcântara A. F.; de C.; Piló-Veloso D.; Raslan D. S. NMR Structural Analysis of Braznitidumine: A New Indole Alkaloid with 1,2,9-Triazabicyclo[7.2.1] System, Isolated from Aspidosperma Nitidum (Apocynaceae). J. Braz. Chem. Soc. 2006, 17, 1274–1280. 10.1590/S0103-50532006000700012. - DOI

[12] Pereira M. M.; Alcântara A. F.; de C.; Piló-Veloso D.; Raslan D. S. NMR Structural Analysis of Braznitidumine: A New Indole Alkaloid with 1,2,9-Triazabicyclo[7.2.1] System, Isolated from Aspidosperma Nitidum (Apocynaceae). J. Braz. Chem. Soc. 2006, 17, 1274–1280. 10.1590/S0103-50532006000700012. - DOI

[13] Ahmed F. S.; Helmy Y. S.; Helmy W. S. Toxicity and Biochemical Impact of Methoxyfenozide/Spinetoram Mixture on Susceptible and Methoxyfenozide-Selected Strains of Spodoptera Littoralis (Lepidoptera: Noctuidae). Sci. Rep. 2022, 12, 6974–6983. 10.1038/s41598-022-10812-w. - DOI - PMC - PubMed

[14] Ahmed F. S.; Helmy Y. S.; Helmy W. S. Toxicity and Biochemical Impact of Methoxyfenozide/Spinetoram Mixture on Susceptible and Methoxyfenozide-Selected Strains of Spodoptera Littoralis (Lepidoptera: Noctuidae). Sci. Rep. 2022, 12, 6974–6983. 10.1038/s41598-022-10812-w. - DOI - PMC - PubMed

[15] Bentué-Ferrer D.; Arvieux C.; Tribut O.; Ruffault A.; Bellissant E. Clinical Pharmacology, Efficacy and Safety of Atazanavir: A Review. Expert Opin. Drug Metab. Toxicol. 2009, 5, 1455–1468. 10.1517/17425250903321514. - DOI - PubMed

[16] Bentué-Ferrer D.; Arvieux C.; Tribut O.; Ruffault A.; Bellissant E. Clinical Pharmacology, Efficacy and Safety of Atazanavir: A Review. Expert Opin. Drug Metab. Toxicol. 2009, 5, 1455–1468. 10.1517/17425250903321514. - DOI - PubMed

Save citation to file

Email citation

Add to Collections

Add to My Bibliography

Your saved search

Create a file for external citation management software

Your RSS Feed

Development of a Nickel-Catalyzed N-N Coupling for the Synthesis of Hydrazides

Affiliations

Development of a Nickel-Catalyzed N-N Coupling for the Synthesis of Hydrazides

Authors

Affiliations

Abstract

Conflict of interest statement

Figures

Similar articles

Cited by

References

Grants and funding

LinkOut - more resources

Full Text Sources