An asymmetric synthesis of (+)-9(11)-dehydroestrone methyl ether (1), a key intermediate for estrogen analogs, is described using a new strategy of consecutive carbocyclizations for the D and C rings of the steroid skeleton based on an asymmetric tandem Claisen-ene sequence. Studies of the stereochemical features of the cyclic enol ether Claisen rearrangement and intramolecular ene reaction are also reported. In the model study of the ene cyclizations, high trans diastereofacial selectivity is found for the alpha-alkylcrotyl and the alpha,beta-dialkylcrotyl ether systems with a methoxycarbonyl group at the acetylenic terminus, which remarkably facilitates the ene cyclization. The Claisen rearrangements of the enol ethers of cyclic ketones were found to exhibit a high level of either anti or syn diastereoselectivity along with high E olefinic stereoselectivity by making judicious use of either 2,6-dimethylphenol or PdCl2(RCN)(2) as the catalyst.