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Volumn 2, Issue 1, 2009, Pages 59-62

A supported copper hydroxide as an efficient, ligand-free, and heterogeneous precatalyst for 1,3-dipolar cycloadditions of organic azides to terminal alkynes

Author keywords

Alkynes; Copper; Cycloaddition; Heterogeneous catalysis; Supported catalysts

Indexed keywords

ALKYNE; ALUMINUM OXIDE; AZIDE; COPPER; COPPER HYDROXIDE; HYDROXIDE; LIGAND;

EID: 61349130803     PISSN: 18645631     EISSN: 1864564X     Source Type: Journal    
DOI: 10.1002/cssc.200800202     Document Type: Article
Times cited : (67)

References (59)
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    • In 2002, the groups of Sharpless and Meldal independently reported that copper salts dramatically accelerate the reaction and make it totally regioselective to the 1,4-regioisomers; see: a V. V. Rostovtsev, L, G. Green, V. V. Fokin, K. B. Sharpless, Angew. Chem. 2002, 114, 2708-2711;
    • In 2002, the groups of Sharpless and Meldal independently reported that copper salts dramatically accelerate the reaction and make it totally regioselective to the 1,4-regioisomers; see: a) V. V. Rostovtsev, L, G. Green, V. V. Fokin, K. B. Sharpless, Angew. Chem. 2002, 114, 2708-2711;
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    • For example, see
    • For example, see:
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    • For examples of the homogeneously catalyzed 1,3-dipolar cycloaddition, see
    • For examples of the homogeneously catalyzed 1,3-dipolar cycloaddition, see:
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    • For examples of the heterogeneously catalyzed 1,3-dipolar cycloaddition, see
    • For examples of the heterogeneously catalyzed 1,3-dipolar cycloaddition, see:
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    • The preparation of a highly dispersed copper hydroxide supported on MgO was unsuccessful because MgO was somewhat soluble in the aqueous CuCI 2 solution
    • 2 solution.
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    • 3 at 550°C.
    • 3 at 550°C.
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    • In the 1,3-dipolar cycloaddition of 1 a to 2a, the reaction rate based on copper species (TOF) on Cu(OH)x/AI2O3 did not change with the loadings of copper species 0.5-2.0 wt
    • 3 did not change with the loadings of copper species (0.5-2.0 wt %).
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    • During the pretreatment, about 10% of the copper(11) species in Cu(OH)x/AI2O3 were reduced to copper(1) species and an almost equimolar amount of 2a with respect to reduced copper species was converted into 1,4-diphenyl-1,3-butadiyne. The degree of reduction of the copper(11) species increased with an increase in the pretreatment period, and all copper(11) species in Cu(OH)x/AI2O3 were reduced to copper(1) species by pretreatment with 2 a for 24 h. The reaction rate for the 1,3-dipolar cycloaddition of 1 a to 2a increased with an increase in the amount of in situ generated copper(1) species. All these results suggest that the copper(11) species in Cu(OH)x/AI2O3 can be reduced to copper(1) species by an alkyne according to Equation (1, 31] and that the in situ generated copper(1) species are true active species for the present 1,3-dipolar cycloaddition. Detailed mechanistic stu
    • [31] and that the in situ generated copper(1) species are true active species for the present 1,3-dipolar cycloaddition. Detailed mechanistic studies are in progress. equation (1)
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    • 2).
    • 2).
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    • [14]
    • [14]
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    • The reaction shown in Equation (2) likely occurred on the copper hydroxide species. R'-D+Cu-OH →← Cu-R' + HDO →← R'-H + Cu-OD
    • The reaction shown in Equation (2) likely occurred on the copper hydroxide species. R'-D+Cu-OH →← Cu-R' + HDO →← R'-H + Cu-OD
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    • It was confirmed that the observed catalysis was also truly heterogeneous for the syntheses of 3 g and 3 k
    • It was confirmed that the observed catalysis was also truly heterogeneous for the syntheses of 3 g and 3 k.


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