📜3-Methoxy-16-Methylene-Estra-1,3,5(10)-Trien-17-One置于sodium Hydroxide,Lithium Aluminium Tetrahydride,双氧水体系中,用 四氢呋喃,叔丁醇 作为反应溶剂,化学反应 4.0H,反应生成 (16S,17R)-3-甲氧基-13,16-二甲基-7,8,9,11,12,14,15,17-八氢-6H-环戊二烯并[a]菲-16,17-二醇
参考文献:Stereoselectivity In The Epoxidation And Cis-Hydroxylation Of 16-Methylene-Estra-1,3,5(10)-Trienes
标题:Stereoselectivity In The Epoxidation And Cis-Hydroxylation Of 16-Methylene-Estra-1,3,5(10)-Trienes
摘要:Epoxidation Of 3-Methoxy-16-Methylene-Estra-1,3,5(10)-Trien-17-One In The Presence Of Alkaline Hydrogen Peroxide Gives Rise To (16R)-And (16S)-Spiro[3-Methoxy-17-Oxoestra-1,3,5(10)-Triene-16,2'-Oxirane] In Similar Proportions. Epoxidation Of The Corresponding 16-Methlene 17 Beta-Alcohol And 16-Methylene-17 Beta-Acetate With M-Chloroperbenzoic Acid Does Not Display Any Significant Directing Effects Associated With Allylic Functionality,Whereas Sharpless Epoxidation Of The 16-Methylene 17 Beta-Alcohol Is Highly Stereoselective,Leading Exclusively To The (16R) Isomer. Cis-Hydroxylation Of The 16-Methylene 17-Ketone With Osmium Tetroxide/4-Methylmorpholine-4-Oxide Proceeds Stereoselectively To Give Mainly 16 Alpha-Hydroxy-16 Beta-Hydroxymethyl-3-Methoxyestra-1,3,5(10)-Trien-17-One. The Isomeric Addition Products Derived From These Reactions Are Correlated By Appropriate Interconversions,And The Assignments Are Corroborated By Comparative Reactivity Of Derived Products.
DOI:10.1016/0039-128X(94)90018-3