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Synlett 2010(11): 1709-1711  
DOI: 10.1055/s-0029-1219964
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© Georg Thieme Verlag Stuttgart ˙ New York

Asymmetric Synthesis of Indolines Bearing a Benzylic Quaternary Stereocenter through Intramolecular Arylcyanation of Alkenes

Jen-Chieh Hsieh, Shiro Ebata, Yoshiaki Nakao*, Tamejiro Hiyama*
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
Fax: +81(75)3832445; e-Mail: yoshiakinakao@npc05.mbox.media.kyoto-u.ac.jp; e-Mail: thiyama@z06.mbox.media.kyoto-u.ac.jp;
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Publication History

Received 1 April 2010
Publication Date:
10 June 2010 (online)

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Abstract

Enantioselective intramolecular arylcyanation of olefins is achieved by a Ni(cod)2/chiral phosphinoxazoline/AlMe2Cl catalyst to give chiral, substituted indoline derivatives bearing a benzylic quaternary stereocenter in high yields with good to excellent enantioselectivities.

Key words

asymmetric synthesis - carbocyanation - C-C bond activation - nickel - indoline

    References and Notes

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11

General Experimental Procedure: An aryl cyanide (0.50 mmol) and a solution of AlMe2Cl (1.04 M in hexane, 0.20 mL, 0.20 mmol) were added sequentially to a solution of Ni(cod)2 (13.8 mg, 50 µmol) and a ligand (50 µmol) in 1,2-dimethoxyethane (0.50 mL) prepared in a 3 mL vial under an argon atmosphere in a dry-box. The vial was sealed with a screw-cap, taken outside the dry-box and heated at 100 ˚C for the time specified Table  [¹] . The resulting mixture was filtered through a silica gel pad, concentrated in vacuo, and purified by flash column chromatography on silica gel to give the corresponding arylcyanation products in the yields listed in Table  [¹]

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See Supporting Information for details

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The presented conditions were completely ineffective for N-methyl-N-(2-cyanophenyl)methacrylamide