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Synthesis 2003(12): 1790-1796
DOI: 10.1055/s-2003-41028
PAPER
© Georg ThiemeVerlag Stuttgart · New York

Synthesis of Allylamines fromAlkynes and Iminium Ions

Susanne Rehn, Armin R. Ofial, Herbert Mayr*
Department Chemie der Ludwig-Maximilians-UniversitätMünchen, Butenandtstr. 5-13 (Haus F), 81377München, Germany
Fax: +49(89)218077717; e-Mail: Herbert.Mayr@cup.uni-muenchen.de;
Further Information

Publication History

Received 10 June 2003
Publication Date:
13 August 2003 (online)

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Abstract

The iminium salt Bn2N+=CH2 SnCl5 - undergoesene reactions with inverse electron demand with alkynes and withthe triple bond of enynes to give benzylideneammonium ions in aprotic solvents.Their hydrolysis yields N-benzylallylaminesin good yields. Mannich reaction products, which are the main productsunder more nucleophilic reaction conditions, have not been detected.

Key words

electrophilic additions - ene reactions - enynes - pericyclic reactions

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1

New address: S. Rehn, Dr. Th. BöhmeKG Chemische Fabrik GmbH & Co., D-82538 Geretsried, Germany.

13

For the spectroscopic characterization,the precipitated iminium salt 2 was filteredoff, washed with a 1:1 mixture of Et2O and CH2Cl2,and dried in vacuo (yield: 93%). 1HNMR (CD3CN, 300 MHz): δ = 5.02(s, 4 H, PhCH 2), 7.34-7.40 (m,4 H, C6H5), 7.45-7.54 (m, 6 H, C6H5),7.95 (t, J HN = 1 Hz,2 H, N+=CH2). 13CNMR (CD3CN, 75.5 MHz): δ = 63.69(t, PhCH2), 130.31, 130.47,131.10 (3 d, C6H5), 131.17 (s, C6H5),169.71 (t, J CN = 11.2Hz, N+=CH2). 119Sn NMR(CD3CN, 100.7 MHz): δ = -673(m).

28

Reactions at temperatures above theboiling points of volatile enophiles were carried out in a pressuretube that was equipped with a magnetic stir bar, sealed with a screw capand heated in an aluminum block on the heating platform of a magneticstirrer.