The Magnesium−Ene Cyclization Stereochemically Directed by an Allylic Oxyanionic Group and Its Application to a Highly Stereoselective Synthesis of (±)-Matatabiether. Allylmagnesium Compounds by Reductive Magnesiation of Allyl Phenyl Sulfides1
journal contributionposted on 13.12.2000, 00:00 by Dai Cheng, Shirong Zhu, Zhifang Yu, Theodore Cohen
The first example of a magnesium−ene cyclization stereochemically directed by an allylic oxyanionic group is demonstrated by a highly stereoselective synthesis of the bicyclic terpene matatabiether 10. The synthetic method is particularly valuable, not only because of the stereochemical control and the utility of the versatile hydroxyl group introduced into the product, but also because the precursor of the allylmagnesium is an allyl phenyl sulfide, which is more stable and more easily prepared in a connective fashion than the usual allyl halide precursor. Since the presence of lithium ions encourages undesirable proton transfer to the cyclized organometallic and is detrimental to the stereochemical control, the conversion of the allylic thioether to the allylmagnesium utilizes a lithium-free method involving direct reductive magnesiation in the presence of the magnesium−anthracene complex.
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fashionpresenceallylmagnesiumcyclizedCyclizationprotonAllyl Phenyl Sulfides 1ApplicationthioetherReductivemagnesiumAllylic Oxyanionic GrouputilitysynthesisMatatabietherorganometallicstereoselectivereductiveCompoundlithiummethodStereochemicallyconversiontransferallyl phenyl sulfideMagnesiumallyl halide precursorMagnesiationallylic oxyanionic grouphydroxylAllylmagnesiumStereoselectivecyclizationbicyclic terpene matatabiether 10stereochemicallymagnesiationSynthesistereochemical control