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[摘要]:An enantioselective synthesis of the Hsp90 inhibitor geldanamycin (I) was achieved in 20 linear steps and 2.0% overall yield from 2-methoxyhydroquinone. The synthesis is highlighted by a regio- and stereoselective hydroboration reaction; a Sc(OTf)3/Et3SiH-mediated pyran ring-opening reaction; an enantioselective crotylation to simultaneously install the C8-C9 (E)-trisubstituted olefin, the C10 and C11 stereocenters; a chelation-controlled asym. metalated acetylide addn.; and an intramol. copper(I)-mediated aryl amidation reaction to close the 19-membered macrolactam. |
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