Reaction SMILES: [BH4-].[Na+].[Si:3]([O:10][C@@H:11]([C@@H:38]([CH3:85])/[CH:39]=[CH:40]\[C@@H:41]([O:77][Si:78]([C:81]([CH3:84])([CH3:83])[CH3:82])([CH3:80])[CH3:79])[CH2:42][C@H:43]([O:69][Si:70]([C:73]([CH3:76])([CH3:75])[CH3:74])([CH3:72])[CH3:71])[C@H:44]([CH3:68])/[CH:45]=[CH:46]/[CH2:47][O:48][C:49]([C:62]1[CH:67]=[CH:66][CH:65]=[CH:64][CH:63]=1)([C:56]1[CH:61]=[CH:60][CH:59]=[CH:58][CH:57]=1)[C:50]1[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=1)[C@@H:12]([CH3:37])[CH2:13][C@@H:14]([CH3:36])/[CH:15]=[CH:16]/[C:17](=[O:35])[C@@H:18]([C@@H:20]1[C@@H:25]([CH3:26])[CH2:24][O:23][CH:22]([C:27]2[CH:32]=[CH:31][C:30]([O:33][CH3:34])=[CH:29][CH:28]=2)[O:21]1)[CH3:19])([C:6]([CH3:9])([CH3:8])[CH3:7])([CH3:5])[CH3:4]>CO.C1COCC1>[Si:3]([O:10][C@@H:11]([C@@H:38]([CH3:85])/[CH:39]=[CH:40]\[C@@H:41]([O:77][Si:78]([C:81]([CH3:84])([CH3:82])[CH3:83])([CH3:80])[CH3:79])[CH2:42][C@H:43]([O:69][Si:70]([C:73]([CH3:76])([CH3:75])[CH3:74])([CH3:71])[CH3:72])[C@H:44]([CH3:68])/[CH:45]=[CH:46]/[CH2:47][O:48][C:49]([C:50]1[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=1)([C:62]1[CH:67]=[CH:66][CH:65]=[CH:64][CH:63]=1)[C:56]1[CH:57]=[CH:58][CH:59]=[CH:60][CH:61]=1)[C@@H:12]([CH3:37])[CH2:13][C@@H:14]([CH3:36])[CH2:15][CH2:16][C:17](=[O:35])[C@@H:18]([C@@H:20]1[C@@H:25]([CH3:26])[CH2:24][O:23][CH:22]([C:27]2[CH:28]=[CH:29][C:30]([O:33][CH3:34])=[CH:31][CH:32]=2)[O:21]1)[CH3:19])([C:6]([CH3:7])([CH3:8])[CH3:9])([CH3:4])[CH3:5]
Reactant: COc1ccc(C2OC[C@H](C)[C@@H]([C@@H](C)C(=O)/C=C/[C@H](C)C[C@H](C)[C@@H](O[Si](C)(C)C(C)(C)C)[C@@H](C)/C=C\[C@H](C[C@H](O[Si](C)(C)C(C)(C)C)[C@H](C)/C=C/COC(c3ccccc3)(c3ccccc3)c3ccccc3)O[Si](C)(C)C(C)(C)C)O2)cc1
Agent: [BH4-]
Agent: [Na+]
Solvent: CO
Solvent: C1CCOC1
Product: COc1ccc(C2OC[C@H](C)[C@@H]([C@@H](C)C(=O)CC[C@H](C)C[C@H](C)[C@@H](O[Si](C)(C)C(C)(C)C)[C@@H](C)/C=C\[C@H](C[C@H](O[Si](C)(C)C(C)(C)C)[C@H](C)/C=C/COC(c3ccccc3)(c3ccccc3)c3ccccc3)O[Si](C)(C)C(C)(C)C)O2)cc1
Reaction time: 1 h
Yield: 75981.3 %

Procedure:
NiCl2.6H2O (0.26 g, 1.09 mmol) then portionwise NaBH4 (0.17 g, 4.49 mmol) were added to a stirred solution of unsaturated ketone 39 (2.60 g, 2.19 μmol) in 80 mL of 3:2 MeOH/THF at 0° C. After 1 h, the reaction mixture was evaporated and filtered through Celite using Et2O (30 mL) as an eluent. The organic phase was concentrated and the residue was purified by flash chromatography (EtOAc/hexane 1:9) to yield 1.98 g of 40 (76%) as a colorless oil: IR (CHCl3) 2955, 2927, 2855, 1711, 1614, 1518, 1461, 1251, 1076, 835, 773 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.46 (m, 6H), 7.27 (m, 1H), 6.85 (m, 2H), 5.60 (m, 2H), 5.43 (s, 1H), 5.40 (m, 1H), 5.27 (m, 1H), 4.52 (m, 1H), 4.11 (dd, J=11.1, 4.7 Hz, 1H), 3.91 (m, 2H), 3.78 (s, 3H), 3.55 (m 2H), 3.50 (m, 1H), 3.35 (m, 1H), 2.67 (m, 1H), 2.58 (m, 1H), 2.51 (m, 1H), 2.41 (m, 1H), 2.01 (m, 1H), 1.68 (m, 3H), 1.41 (m, 5H), 1.23 (d, J=7.1 Hz, 3H), 0.96 (d, J=6.7 Hz, 3H), 0.90 (s, 9H), 0.89 (s, 9H), 0.88 (m, 1H), 0.87 (m, 3H), 0.80 (s, 9H), 0.78 (m, 6H), 0.10 (s, 3H), 0.08 (s, 3H), 0.04 (s, 3H), 0.03 (s, 6H), 0.01 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 211.9, 159.8, 144.5, 144.3, 134.4, 132.9, 132.4, 130.9, 128.6, 127.9, 127.8, 127.7, 127.1, 126.8, 113.4, 100.8, 86.7, 83.1, 79.9, 72.8, 72.2, 66.4, 65.1, 55.1, 48.3, 42.3, 41.5, 41.2, 38.1, 35.7, 35.0, 31.2, 29.8, 29.7, 26.2, 25.92, 25.87, 20.2, 19.4, 18.4, 18.1, 18.0, 15.2, 13.2, 12.1, 9.6, −3.0, −3.5, −3.7, −4.2, −4.28, −4.34; LRMS (ESI) 1211.9 (30 mL), 1031.8, 870.4, 684.3, 366.4, 243.1; HRMS (ESI) calcd for C72H112O8Si3Na 1211.7563 (30 mL), found 1211.7616; [α]20D +1.6 (c 0.50, CHCl3).