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Synlett 2009(19): 3211-3213  
DOI: 10.1055/s-0029-1218297
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Silver-Catalyzed Intermolecular Hydroamination of Alkenes and 1,3-Dienes

Xavier Giner, Carmen Nájera*
Departamento de Química Orgánica, Facultad de Ciencias and Instituto de Síntesis Orgánica (ISO), Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain
Fax: +34(96)5903549; e-Mail: cnajera@ua.es;
Further Information

Publication History

Received 23 July 2009
Publication Date:
15 October 2009 (online)

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Abstract

Silver triflate is used as efficient catalyst for the intermolecular addition of 4-toluenesulfonamide to alkenes under thermal or microwave heating. The hydroamination of 1,3-dienes can be performed at 85 ˚C with low catalyst loading (0.1-5 mol%) or at room temperature using 1 mol% of AgOTf, the use of HOTf affording similar results.

Key words

alkenes - conjugated dienes - hydroamination - sulfon­amides - silver catalysts

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8

General Procedure for the Hydroamination of Alkenes and Dienes
To a mixture of silver salt (see Tables  [¹] and  [²] ) and sulfonamide (171 mg, 1 mmol) in dry solvent (2 mL, see Tables  [¹] and  [²] ) was added the alkene or 1,3-diene (4 mmol) with magnetic stirring in a sealed tube under argon atmosphere in the dark. For neat experiments (see Table  [²] , entries 6-8) no solvent was added. After the corresponding reaction time under the conditions indicated in Tables  [¹] and  [²] (for microwave heating the vessel was sealed with a pressure lock, and the mixture was heated at 90 ˚C in a CEM Discover MW reactor at 70 W, 0.69 bar with air stream cooling during 30 min), to the reaction mixture cooled at r.t. was added H2O (2 mL) and brine (2 drops). The organic layer was separated, and the aqueous phase was extracted with EtOAc (2 × 10 mL). All organic phases were mixed, dried with MgSO4, and evaporated. Pure products were obtained by recrystallization or by flash chromatography.

9

Crystallographic data (excluding structure factors) have been deposited with the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk./data_request/cif as supplementary publication no. CCDC 748465 [unit cell parameters: a 12.2371 (16), b 17.627 (2), c 7.9272 (11),
β 105.117 (3), space group P21/c].