Chiral gold(I) phosphite complexes are readily prepared modularly from 3,3′-bis(triphenylsilyl)-1,1′-bi-2-naphthol. These chiral gold(I) phosphite complexes are very reactive precatalysts for the [4+2] cycloaddition of aryl-substituted 1,6-enynes with enantiomeric ratios ranging from 86 : 14 up to 94 : 6.