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Synlett 2010(3): 419-422  
DOI: 10.1055/s-0029-1218555
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Gold(I)-Catalyzed Intermolecular Hydroamination of Allenes with Arylamines

Alethea N. Duncan, Ross A. Widenhoefer*
French Family Science Center, Duke University, Durham, NC 27708, USA
Fax: +1(919)660-1605; e-Mail: rwidenho@chem.duke.edu;
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Publikationsverlauf

Received 21 August 2009
Publikationsdatum:
07. Januar 2010 (online)

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Abstract

A mixture of [P(t-Bu)2-o-biphenyl]AuCl and AgOTf catalyzes the intermolecular hydroamination of monosubstituted and 1,1- and 1,3-disubstituted allenes with primary and secondary aryl­amines.

Key words

allylations - allenes - amines - homogenous catalysis - ­regioselectivity

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14

Experimental Procedure and Spectroscopic Data for the Gold(I)-Catalyzed Hydroamination of 1 with o -Bromo-aniline (Table 2, entry 2): Dioxane (0.50 mL) was added to a mixture of o-bromoaniline (39 mg, 0.23 mmol), (3)AuCl (6.2 mg, 1.1 × 10-² mmol), and AgOTf (2.8 mg, 1.1 × 10-² mmol) and the resulting suspension was stirred for 10 min at r.t. 3-Methyl-1,2-butadiene (1; 29 mg, 0.43 mmol) was added via syringe and the resulting mixture was stirred at 45 ˚C for 24 h. Column chromatography of the reaction mixture (SiO2; hexanes-EtOAc, 15:1) gave N-(3-methyl-2-butenyl)-o-bromoaniline (48 mg, 87%) as a pale yellow oil. ¹H NMR (400 MHz, CDCl3): δ = 7.41 (dd, J = 1.5, 8.5 Hz, 1 H), 7.17 (dd, J = 1.5, 7.8 Hz, 1 H), 6.62 (dd, J = 1.0, 8.3 Hz, 1 H), 6.55 (dt, J = 1.5, 7.5 Hz, 1 H), 5.31-5.35 (m, 1 H), 4.23 (br s, 1 H), 3.72 (d, J = 6.8 Hz, 2 H), 1.76 (d, J = 1.0 Hz, 3 H), 1.72 (s, 3 H). ¹³C{¹H} NMR (100 MHz, CDCl3): δ = 145.1, 136.1, 132.3, 128.4, 121.1, 117.5, 111.4, 109.7, 41.9, 25.7, 18.1. HRMS: m/z [M+] calcd for C11H14BrN: 239.0310; found: 239.0313.