Direct copper(I)-catalyzed cycloaddition of organic azides with TMS-protected alkynes

Synlett

Volumn , Issue 12, 2010, Pages 1873-1877

  Cuevas, Félix ^a   Oliva, Ana I ^a   Pericàs, Miquel A ^a,b  

^a INSTITUTE OF CHEMICAL RESEARCH OF CATALONIA ICIQ   (Spain)

^b UNIVERSITY OF BARCELONA   (Spain)

Author keywords

alkynes; azides; click chemistry; cycloaddition; tandem reaction

Indexed keywords

AZIDE; CUPROUS ION; TRIMETHYLSILYL DERIVATIVE;

ARTICLE; BIOCATALYST; BIOTRANSFORMATION; CHEMICAL MODIFICATION; CHEMICAL STRUCTURE; CYCLOADDITION; DESILATION; HYDROLYSIS; METHODOLOGY; PROTECTION;

EID: 77954844631     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-0030-1258120     Document Type: Article

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34. General Procedure for the Tandem DesilylationCuAAC Reaction of 1-Trimethylsilyl-1-alkynes Method A A mixture of the alkyne (0.24 mmol), CuBr (0.04 mmol, 15 mol%), benzylazide (0.26 mmol), and Et3N (0.24 mmol) in DMF (0.5 mL) was stirred at 100 °C for the time indicated in Tables 1 and 2. The reaction mixture was cooled at r.t., a sat. solution of NH4Cl was added and extracted with EtOAc. The organic layer was washed with H2O, dried over Na2SO4, filtered, and concentrated under reduced pressure. Purification by flash chromatography, silica gel, gradient hexane to EtOAc. Method B As described in method A, but additional H2O (2 equiv) was added. 1-Benzyl-4-phenyl-1H-1,2,3- trizole (3a) From 1-phenyl-2-trimethylsilylacetylene (1a, 27 mg, 30 mL, 0.15 mmol), CuBr (3.3 mg, 0.02 mmol), benzylazide (22 mg, 21 mL, 0.17 mmol), and Et3N (16 mg, 22 mL, 0.16 mmol) in DMF (0.5 mL), afforded the titled compound (method A: 34 mg, 94% yield; method B: 97%) as a white solid; mp 134 136 °C. 1H NMR (400 MHz, CDCl3): d = 7.82 (d, J = 7.2 Hz, 2 H), 7.69 (s, 1 H), 7.37 (m, 5 H), 7.33 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): d = 148.35, 134.95, 130.78, 129.31, 129.01, 128.93, 128.34, 128.22, 125.88, 119.86, 54.34 ppm. HRMS (ESI+): m/z calcd for [M + Na]+: 258.1007; found: 258.1001.
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