Rhodium-Catalyzed Arylative Cyclization Reaction of Diynes with Arylboronic Acids

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.

rhodium - cyclizations - addition reactions - arylboronic acids - diynes

References and Notes

For reviews, see:

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<A NAME="RU04707ST-8">8</A>

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

<A NAME="RU04707ST-9">9</A>

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.

For regioselectivities of transition-metal-catalyzed reactions of unsymmetrical 1,6-diynes, see:

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<A NAME="RU04707ST-11">11</A>

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.

<A NAME="RU04707ST-12A">12a</A> Miura T. Shimada M. Murakami M. J. Am. Chem. Soc.  2005,  127:  1094 

<A NAME="RU04707ST-12B">12b</A> Miura T. Shimada M. Murakami M. Chem. Asian J.  2006,  1:  868 

<A NAME="RU04707ST-13A">13a</A> Lautens M. Mancuso J. J. Org. Chem.  2004,  69:  3478 

<A NAME="RU04707ST-13B">13b</A> Lautens M. Marquardt T. J. Org. Chem.  2004,  69:  4607