Direct synthesis of (+)-erogorgiaene through a kinetic enantiodifferentiating step
Direct synthesis of (+)-erogorgiaene through a kinetic enantiodifferentiating step
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DOI：
10.1002/anie.200462227
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发表时间：
2005-01-01
影响因子：
16.6
通讯作者：
Walji, AM
中科院分区：
文献类型：
--
作者：
Davies, HML;Walji, AM
(+)-Erogorgiaene is a member of the marine diterpenes isolated from the West Indian sea whip Pseudopterogorgia elisabethae and displays promising activity against Mycobacterium tuberculosis H37Rv.[1] Several important biologically active secondary metabolites have been isolated from the Pseudopterogorgia corals.[2] Consequently, there has been extensive activity directed towards the synthesis of these natural products.[3] Even though these compounds are not especially complex, a major challenge associated with their synthesis has been the control of the three stereocenters (marked in red, 1–3, Scheme 1), common to all of them. The stereocontrol has been challenging because of the lack of functional groups near to the stereogenic centers. This has meant that many of the syntheses have been very lengthy with considerable functional group interconversions, and even then the stereocontrol has been less than satisfactory.[3] The only reported synthesis of (+)-erogorgiaene (1), described by Hoveyda and co-workers, employed a chiral-catalyst-controlled conjugate addition in a sequential manner to set up the desired stereocenters.[4]Here we illustrate through the enantioselective synthesis of (+)-erogorgiaene (1) a potentially general strategy to the synthesis of this class of diterpenes. The key step is our recently discovered combined CÀH activation/Cope rearrangement catalyzed by dirhodium tetraprolinate [Rh2 (dosp) 4](dosp=(N-dodecylbenzenesulfonyl) prolinate),
