Synlett 2012; 23(7): 1069-1073
DOI: 10.1055/s-0031-1290758
letter
© Georg Thieme Verlag Stuttgart · New York

Carbon–Nitrogen Bond Formation between Allyl Silyl Ether and Hydrazide Promoted by Mercuric Triflate Catalyst

Hirofumi Yamamoto*
a   Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-cho, Tokushima 770-8514, Japan, Fax: +81(88)6553051   Email: hirofumi@ph.bunri-u.ac.jp
,
Naoto Yamasaki
a   Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-cho, Tokushima 770-8514, Japan, Fax: +81(88)6553051   Email: hirofumi@ph.bunri-u.ac.jp
,
Shingo Yoshidome
a   Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-cho, Tokushima 770-8514, Japan, Fax: +81(88)6553051   Email: hirofumi@ph.bunri-u.ac.jp
,
Ikuo Sasaki
a   Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-cho, Tokushima 770-8514, Japan, Fax: +81(88)6553051   Email: hirofumi@ph.bunri-u.ac.jp
,
Kosuke Namba
b   Division of Chemistry, Graduate School of Science, Hokkaido University, Kita-ku, Sapporo 060-0810, Japan
,
Hiroshi Imagawa
a   Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-cho, Tokushima 770-8514, Japan, Fax: +81(88)6553051   Email: hirofumi@ph.bunri-u.ac.jp
,
Mugio Nishizawa
a   Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-cho, Tokushima 770-8514, Japan, Fax: +81(88)6553051   Email: hirofumi@ph.bunri-u.ac.jp
› Author Affiliations
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

 
  • References

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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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