A DABCO-catalyzed highly regio-and stereoselective syn-1, 4-bromolactonization of conjugated enynes was discovered. The 1, 4-addition occurred selectively over 1, 2-addition for most enynes. In contrast to anti 1, 2-addition to alkenes, where two adjacent stereogenic centers are created, 1, 4-addition across conjugated enynes can produce a stereogenic center and an axially chiral allene simultaneously. Enynes with Z and E configurations ...