Samuel Danishefsky

Samuel DanishefskyChristian AichingerDenksport, October 2010

Total syntheses

Spirotryprostatin B1) von Nussbaum, F.; Danishefsky, S. J. Angew. Chem. Int. Ed. 2000, 39, 2175-2178.

11-O-DebenzoyltashironinOH1) Zn(CN) 2 , HCl2) TsCl3) BnBr, K 2 CO 3OOBn1) mCPBA2) NEt 3OHOBn1) NBS2) TBSClBrOTBSOBnOH56% (3 steps)OTs98% (2 steps)OTs74% (2 steps)OTsHOSnBu 3Pd 2 (dba) 3tBu 3 P77%OHOHOBn1) MsCl2) Me 2 Cu(CN)Li 23) TBAFOHOTBSOBn1) DMP2) ZnEt 2 , Ti(OiPr) 4TBSOOHOTBSOBnOTs84% (3 steps) 90% (2 steps)OTBSOTsOTsPhI(OAc) 2OOBnO µw65%OTsOOBnOOTs=OOOBnOTs1) NaBH 42) TMS-Im83% (2 steps)TMSOOOBnOTs1) mCPBA2) P(Ph 3 ) 3 RhCl, H 228%; 53% brsm (2 steps)HOOOH1) DMP2) HF-py; TBAF3) H 2 , Pd/CTMSOOOBnLiEt 3 BHTMSOOOBnHOO11-O-debenzoyl tashironin76% (3 steps)HOOH32%OOTs2) Cook, S. P.; Polara, A.; Danishefsky, S. J. J. Am. Chem. Soc. 2006, 128, 16440-16441.

IndolizomycinOOHN Isolated 1985 Unstableindolizomycin First and only synthesis by Danishefsky