M.C. White, Chem 153 Hydrozirconation -294- Week of november 18. 2002 Synthetic applications Hydrozirconation/transmetalation sequence in the total synthesis of Fostriecin Jacobsen ACIEE 2001 (40)3667 L [Cp2Zr(H)CI], CHCI 2. Me, Zn(-78 C). 10 minR Pro Zr(Ci)Cp2 ZnMe 45% Hydrozirconation/bromination sequence in the total synthesis of FK 506. Schreiber JACS 1990(112)5583 TIPSO 2. NBS, rt, 25 min Meo Me Hydrozirconation/Negishi coupling sequence in the total synthesis of FR901464 Jacobsen JACS 2000(122)10482 Cp(Ciz I 1. Cp Zr(h)CII ZnCl THE, OoC THF. 0C 3. Pd(PPh3)4(6.5mo%) TESO TESO btained via hydrozirconation/ iodination sequenceM.C. White, Chem 153 Hydrozirconation -294- Week of November 18, 2002 Synthetic applications i-PrO O H Me O O ZrIV Me Cl Me2Zn Me O R O ZnMe R Zr(Cl)Cp2 i-PrO O OH O 1. [Cp2Zr(H)Cl], CH2Cl2 2. Me2Zn (-78oC), 10 min 3. R ~ 45% Hydrozirconation/transmetalation sequence in the total synthesis of Fostriecin. Jacobsen ACIEE 2001 (40) 3667. Hydrozirconation/bromination sequence in the total synthesis of FK 506. Schreiber JACS 1990 (112) 5583. Me MeO TIPSO MeO TIPSO Br Me MeO TIPSO Zr(Cl)Cp2 Me 1. [Cp2Zr(H)Cl](3 eq), benzene, 30-40oC 2. NBS, rt, 25 min R 86% Hydrozirconation/Negishi coupling sequence in the total synthesis of FR901464. Jacobsen JACS 2000 (122) 10482. O I H O TESO O I O TESO Cp2(Cl)Zr 2. ZnCl2, THF, 0oC 3. Pd(PPh3)4 (6.5mol%) O N3 I obtained via hydrozirconation/ iodination sequence O I O TESO O N3 1. [Cp2Zr(H)Cl], THF, 0oC 80%