Zirconium-catalyzed methylalumination of heterosubstituted arylethynes: Factors affecting the regio-, stereo-, and chemoselectivities

The Zr-catalyzed methylalumination of heterosubstituted arylethynes containing O, S, Cl, and Si can proceed in high yields (>70%) and in a highly regio- and stereoselective manner (⩾98–99%), although SO2Ph, Br, and Cl in a benzylic position present serious chemoselectivity-related problems. The low regioselectivity of 60% initially observed with o-ethynylphenol (1a) has been elevated to ⩾98% through the use of either a catalytic amount of Zr(ebi)Cl2 or Zr(2-Me-Ind)2Cl2 or, more conveniently, the stoichiometric amount of ZrCp2Cl2, ZrCp2MeCl, or ZrCp2Me2 in conjunction with the use of a deficient amount (0.9 molar equiv.) of I2 for subsequent iodinolysis.

Graphical abstractThe Zr-catalyzed methylalumination of heterosubstituted arylethynes containing O, S, Cl, and Si can proceed in high yields (>70%) and in a highly regio- and stereoselective manner (⩾98–99%), although SO2Ph, Br, and Cl in a benzylic position present serious chemoselectivity-related problems. The low regioselectivity of 60% initially observed with o-ethynylphenol (1a) has been elevated to ⩾98% through the use of either a catalytic amount of Zr(ebi)Cl2 or Zr(2-Me-Ind)2Cl2 or, more conveniently, the stoichiometric amount of ZrCp2Cl2, ZrCp2MeCl, or ZrCp2Me2 in conjunction with the use of a deficient amount (0.9 molar equiv.) of I2.Figure optionsDownload full-size imageDownload as PowerPoint slide