Selective formation of 1,4-disubstituted triazoles from ruthenium-catalyzed cycloaddition of terminal alkynes and organic azides

Scope and reaction mechanism

Pei Nian Liu, Juan Li, Fu Hai Su, Kun Dong Ju, Li Zhang, Chuan Shi, Herman H Y Sung, Ian D. Williams, Valery V. Fokin, Zhenyang Lin, Guochen Jia

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

The catalytic activity of a series of ruthenium complexes lacking cyclopentadienyl ligands has been evaluated for the cycloaddition of terminal alkynes and azides to give selectively 1,4-disubstituted 1,2,3-triazoles. The complex RuH(η 2-BH 4)(CO)(PCy 3) 2 was found to be an effective catalyst for the cycloaddition reactions. In the presence of RuH(η 2-BH 4)(CO)(PCy 3) 2, primary and secondary azides reacted with a range of terminal alkynes containing various functionalities to selectively produce 1,4-disubstituted 1,2,3-triazoles. The ruthenium-catalyzed azide-alkyne cycloaddition appears to proceed via a Ru-acetylide species as the key intermediate, which undergoes formal cycloaddition with an azide to give a ruthenium triazolide complex. The 1,4-disubstituted 1,2,3-triazole product is generated by metathesis of the triazolide complex with a terminal alkyne. In support of the reaction mechanism, the acetylide complex Ru(C≡CCMe 3) 2(CO)(PPh 3) 3 reacts cleanly with benzyl azide to give a ruthenium triazolide complex, which reacts with excess tert-butylacetylene in the presence of PPh 3 to give 4-tert-butyl-1-benzyl-1,2,3-triazole and the diacetylide complex Ru(C≡CCMe 3) 2(CO)(PPh 3) 3. The mechanism is also supported by DFT calculations.

Original languageEnglish
Pages (from-to)4904-4915
Number of pages12
JournalOrganometallics
Volume31
Issue number13
DOIs
Publication statusPublished - 9 Jul 2012
Externally publishedYes

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azides (organic)
Triazoles
Alkynes
Ruthenium
Azides
Cycloaddition
cycloaddition
alkynes
ruthenium
Carbon Monoxide
metathesis
catalytic activity
Discrete Fourier transforms
Catalyst activity
catalysts
ligands
Ligands
products
Catalysts

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Selective formation of 1,4-disubstituted triazoles from ruthenium-catalyzed cycloaddition of terminal alkynes and organic azides : Scope and reaction mechanism. / Liu, Pei Nian; Li, Juan; Su, Fu Hai; Ju, Kun Dong; Zhang, Li; Shi, Chuan; Sung, Herman H Y; Williams, Ian D.; Fokin, Valery V.; Lin, Zhenyang; Jia, Guochen.

In: Organometallics, Vol. 31, No. 13, 09.07.2012, p. 4904-4915.

Research output: Contribution to journalArticle

Liu, PN, Li, J, Su, FH, Ju, KD, Zhang, L, Shi, C, Sung, HHY, Williams, ID, Fokin, VV, Lin, Z & Jia, G 2012, 'Selective formation of 1,4-disubstituted triazoles from ruthenium-catalyzed cycloaddition of terminal alkynes and organic azides: Scope and reaction mechanism', Organometallics, vol. 31, no. 13, pp. 4904-4915. https://doi.org/10.1021/om300513w
Liu, Pei Nian ; Li, Juan ; Su, Fu Hai ; Ju, Kun Dong ; Zhang, Li ; Shi, Chuan ; Sung, Herman H Y ; Williams, Ian D. ; Fokin, Valery V. ; Lin, Zhenyang ; Jia, Guochen. / Selective formation of 1,4-disubstituted triazoles from ruthenium-catalyzed cycloaddition of terminal alkynes and organic azides : Scope and reaction mechanism. In: Organometallics. 2012 ; Vol. 31, No. 13. pp. 4904-4915.
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abstract = "The catalytic activity of a series of ruthenium complexes lacking cyclopentadienyl ligands has been evaluated for the cycloaddition of terminal alkynes and azides to give selectively 1,4-disubstituted 1,2,3-triazoles. The complex RuH(η 2-BH 4)(CO)(PCy 3) 2 was found to be an effective catalyst for the cycloaddition reactions. In the presence of RuH(η 2-BH 4)(CO)(PCy 3) 2, primary and secondary azides reacted with a range of terminal alkynes containing various functionalities to selectively produce 1,4-disubstituted 1,2,3-triazoles. The ruthenium-catalyzed azide-alkyne cycloaddition appears to proceed via a Ru-acetylide species as the key intermediate, which undergoes formal cycloaddition with an azide to give a ruthenium triazolide complex. The 1,4-disubstituted 1,2,3-triazole product is generated by metathesis of the triazolide complex with a terminal alkyne. In support of the reaction mechanism, the acetylide complex Ru(C≡CCMe 3) 2(CO)(PPh 3) 3 reacts cleanly with benzyl azide to give a ruthenium triazolide complex, which reacts with excess tert-butylacetylene in the presence of PPh 3 to give 4-tert-butyl-1-benzyl-1,2,3-triazole and the diacetylide complex Ru(C≡CCMe 3) 2(CO)(PPh 3) 3. The mechanism is also supported by DFT calculations.",
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T1 - Selective formation of 1,4-disubstituted triazoles from ruthenium-catalyzed cycloaddition of terminal alkynes and organic azides

T2 - Scope and reaction mechanism

AU - Liu, Pei Nian

AU - Li, Juan

AU - Su, Fu Hai

AU - Ju, Kun Dong

AU - Zhang, Li

AU - Shi, Chuan

AU - Sung, Herman H Y

AU - Williams, Ian D.

AU - Fokin, Valery V.

AU - Lin, Zhenyang

AU - Jia, Guochen

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