Ether-directed diastereoselectivity in Overman rearrangement of δ-methoxy and δ-TBDMSO substituted allylic trichloroacetimidates has been explored using PtCl2, PtCl4, AuCl and AuCl3 catalysts in comparison with commonly used Pd (II) catalysts. For both substrates the use of PtCl2 catalyst gave notably improved anti/syn-ratio of 1, 2-aminoalcohol derivatives (anti/syn= 11: 1 for δ-methoxy; 6: 1 for δ-TBDMSO) compared to all metal catalysts known ...