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Construction of intermediate 86 Continued 1. H2, Pd(oH), EtOAC, 25C 2. LAIH. THF. 0C (92% for steps 1 and 2) OTPS HH H 0-CO2Me 3.t-BuPh2SiCl, Et,N 4DMAP,cH2Cz,25°C 4. +-BuMe2 SIOTf, 2, 6-lutidine, (95% for steps 3 and 4) 1. CSA, CH2Cl2: MeOH (1: 1),0C 2. TBSCI,imid,DMF,0° 3. NMO, TPAP (cat ) CH3CN, 25C 1. EtSH, Zn(OTD2, CH2Cl2, 25C OTBS 2.CSA.MeOH.25℃ ES入H。、Me OTPS JK (68% overall)O 122 Me OBn K H H O H J O H I H O O CO2Me 1. H2, Pd(OH)2, EtOAc, 25 oC 2. LAlH4 , THF, 0 oC (92% for steps 1 and 2) 3. t-BuPh2SiCl, Et3N, 4-DMAP, CH2Cl2 , 25 oC 4. t-BuMe2SiOTf, 2,6-lutidine, CH2Cl2 , 0 oC (95% for steps 3 and 4) O 124 Me OTBS K H H O H J O H I H O O OTPS 1. CSA, CH2Cl2 :MeOH (1:1), 0 oC 2. TBSCl, imid., DMF, 0 oC 3. NMO, TPAP (cat.), CH3CN, 25 oC O 125 Me OTBS K H H O H J O I H O OTPS OTBS 1. EtSH, Zn(OTf)2 , CH2Cl2 , 25 oC 2. CSA, MeOH, 25 oC 3. SO3 pyr., Et3N, DMSO, CH2Cl2 , 0 oC (68% overall) O O O H H OTBS EtS H Me I EtS H H O J K OTPS Key Intermediate 86 Construction of Intermediate 86 Continued
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