Synlett 2007(13): 2029-2032  
DOI: 10.1055/s-2007-984879
LETTER
© Georg Thieme Verlag Stuttgart · New York

Rhodium-Catalyzed Arylative Cyclization Reaction of Diynes with Arylboronic Acids

Tomoya Miura, Motoshi Yamauchi, Masahiro Murakami*
Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto 615-8510, Japan
Fax: +81(75)3832748; e-Mail: murakami@sbchem.kyoto-u.ac.jp;
Further Information

Publication History

Received 10 May 2007
Publication Date:
12 July 2007 (online)

Abstract

Diynes having malonate-based tethers react with aryl­boronic acids in the presence of a rhodium(I) catalyst to give 1,2-dialkylidenecycloalkanes. The regioselectivity of the initial carbo­rhodation depends on the sterics and the directing nature of the alkyne substituents.

8

Phenylboroxine was used instead of phenylboronic acid to avoid proton scrambling.

9

General Procedure for the Cyclization Reaction of 1a with 2: To an oven-dried, Ar-purged flask were added [Rh(OH)(cod)]2 (2.3 mg, 5.0 µmol, 5 mol% Rh), 1a (47.3 mg, 0.2 mmol), 2 (0.4 mmol), and dioxane-H2O (2.0 mL:0.1 mL). The reaction mixture was stirred at r.t. for 12 h, and quenched with addition of H2O (5 mL). The aqueous layer was extracted with EtOAc (5 × 6 mL). The combined extracts were washed with brine and dried over MgSO4. The solvent was removed under reduced pressure and the residue was purified by preparative TLC (hexane-EtOAc) to give 3.

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A reaction using unsymmetrical 1,6-diyne disubstituted with methyl and phenyl groups (4, R = Ph) proceeded at 100 °C to afford a complex mixture of products, although the reason is unclear.