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Synlett 2012; 23(7): 1069-1073
DOI: 10.1055/s-0031-1290758
DOI: 10.1055/s-0031-1290758
letter
Carbon–Nitrogen Bond Formation between Allyl Silyl Ether and Hydrazide Promoted by Mercuric Triflate Catalyst
Further Information
Publication History
Received: 24 January 2012
Accepted after revision: 14 February 2012
Publication Date:
05 April 2012 (online)
Abstract
An efficient method for carbon–nitrogen bond formation between ally silyl ethers and N,N-acyltosylhydrazine was developed under very mild conditions using 2 mol% of mercuric triflate [Hg(OTf)2] as a catalyst. This method does not require the use of any ligand system or supplementary additives and is applicable to the preparation of various N-allylhydrazides with good to excellent yields.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
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- 12 General Procedure: To a solution of TBDPS ether 1h (1 g, 3.0 mmol) and N,N-acyltosylhydrazine (4, 1.01 g, 4.5 mmol) in MeNO2 (15 mL) was added a 0.1 M MeCN solution of Hg(OTf)2 (0.6 mL, 0.06 mmol) at r.t. under argon atmosphere. After stirring for 4 h at r.t., the reaction mixture was quenched with sat. aq NaHCO3. The organic materials were extracted with EtOAc, and then washed with brine. The organic phase was dried over Na2SO4, and the filtrates were concentrated under reduced pressure. The residue was subjected to column chromatography on silica gel using hexane and EtOAc (8:1) to give N,N-acyltosylhydrazine adduct 5 (754 mg, 82%) as a white solid.Analytical Data for Compound 5: white solid. FTIR (neat): νmax = 3314, 3068, 3025, 2935, 2862, 2835, 1706, 1596 cm–1. 1H NMR (400 MHz, DMSO, 60 °C): δ = 1.50 (2 H, m), 1.68 (2 H, m), 1.97 (2 H, m), 2.13 (3 H, s), 2.40 (3 H, s), 3.83 (1 H, m), 5.57 (1 H, m), 5.84 (1 H, ddt, J = 10.4, 3.6, 1.6 Hz), 6.21 (NH, br d, J = 2.0 Hz), 7.40 (2 H, br d, J = 8.4 Hz), 7.85 (2 H, br d, J = 8.4 Hz). 13C NMR (100 MHz, DMSO, 60 °C): δ = 18.88, 21.42, 23.76, 25.29, 27.10, 54.42, 125.87, 128.77, 128.84, 129.68, 129.78, 131.26, 136.78, 144.85, 172.99. MS (CI): m/z [M + H]+ calcd for C15H21O3N2S: 309.1273; found: 309.1274
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