Construction of intermediate 87 Continued 1. LiN(SiMe3)2, HMPA, THF Me -78 C; then Tf2NPh, 25C D XoHWHO Me. TBSo、:CHo 150 Nozaki yama 1KH,CS2,E2O,25°C Kishi CrCl2, NiCk(cat ), DMF, 2. n-Bu SnH, AIBN 25°c, ultrasound PhH80° (64%overall (60% overall) o物90mn1m30c TBSO E FG then NaOH.H20℃TBsO、 2. Et SIOTf, 2, 6-lutidine Pvo′0 CH2C20°c (79% overall) 1. Dibal-H, CH2 Ch, -78C 3.( MeO)P(O)CH2CO-Me KN(SiMe 3)2, 18-crown-6, THF, 0C (82% overall) 1. CSA, MeOH, 25C OBn 2. KH,Et20, 25%C (90% overall) TBS. EeOc. TESO O O OBn OBn Me Me H H H Me O E F G H H O 100 Me 1. LiN(SiMe3 )2 , HMPA, THF -78 oC; then Tf2NPh, 25 oC D TBSO CHO Me PivO O O O OBn OBn Me Me H O E F G H H 150 Me D TBSO PivO Me HO CrCl2 , NiCl2 (cat.), DMF, 25 oC, ultrasound (64% overall) 2. 1. KH, CS2 , Et2O, 25 oC; then MeI 2. n-Bu3SnH, AIBN, PhH, 80 oC (60% overall) TBSO O O O O H H H Me Me H Me Me Me D E F G OBn OBn H PivO H H Me 96 TBSO O O O O O H H H H Me Me H H Me Me Me D E F G OBn OBn H PivO TES 151 1. BH3 -THF, THF, -30 oC; then NaOH, H2O2 , 0 oC 2. Et3SiOTf, 2,6-lutidine, CH2Cl2 , 0 oC (79% overall) TBSO O O O O O H H H H Me Me H H Me Me Me D E F G OBn OBn H M TES eO2C 152 1. Dibal-H, CH2Cl2 , -78 oC 2. DMP, CH2Cl2 , 25 oC 3. (MeO)2P(O)CH2CO2Me, KN(SiMe3 )2 , 18-crown-6, THF, 0 oC (82% overall) TBSO O O O O O H H H H H Me Me H H Me Me Me C D E F G OBn OBn H MeO2C 1. CSA, MeOH, 25 oC 2. KH, Et2O, 25 oC (90% overall) 153 Construction of Intermediate 87 Continued Nozaki Hiyama Kishi