Sodium borohydride → HCID 87286797, compound

HRID 2428059Notes

Reaction equation

HRID 2428059 reaction equation
[CH2:1]([O:3][C:4](=[O:68])[CH:5]=[CH:6][C@H:7]([CH3:67])[C@H:8]([O:57][CH2:58][C:59]1[CH:64]=[CH:63][C:62]([O:65][CH3:66])=[CH:61][CH:60]=1)[C@@H:9]([CH3:56])[CH:10]=[CH:11][C@@H:12]([O:48][Si:49]([C:52]([CH3:55])([CH3:54])[CH3:53])([CH3:51])[CH3:50])[CH2:13][C@H:14]([O:40][Si:41]([C:44]([CH3:47])([CH3:46])[CH3:45])([CH3:43])[CH3:42])[C@H:15]([CH3:39])[CH:16]=[CH:17][CH2:18][O:19][C:20]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[CH3:2].[BH4-].[Na+]>CO.C1COCC1>[CH2:1]([O:3][C:4](=[O:68])[CH2:5][CH2:6][C@H:7]([CH3:67])[C@@H:8]([O:57][CH2:58][C:59]1[CH:64]=[CH:63][C:62]([O:65][CH3:66])=[CH:61][CH:60]=1)[C@@H:9]([CH3:56])[CH:10]=[CH:11][C@@H:12]([O:48][Si:49]([C:52]([CH3:53])([CH3:54])[CH3:55])([CH3:50])[CH3:51])[CH2:13][C@H:14]([O:40][Si:41]([C:44]([CH3:47])([CH3:46])[CH3:45])([CH3:42])[CH3:43])[C@H:15]([CH3:39])[CH:16]=[CH:17][CH2:18][O:19][C:20]([C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1)([C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1)[C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[CH3:2]

Participants

5

Reactant 2

HCID 4311764Sodium borohydrideHCID 87286943HCID 87286943, compound

Product 1

HCID 87286797HCID 87286797, compoundYield 97.1%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of unsaturated ester 65 (2.02 g, 2.10 μmol) in MeOH (10 ml), THF (1 ml) at 0° C. was added 0.25 g of NiCl·6H2O then portionwise NaBH4 (0.16 g). After 1 h, the reaction mixture was evaporated and filtered with Celite using Et2O as an eluent (5 ml). The organic phase was concentrated and the residue was purified by flash chromatography (EtOAc/Hexane 1:9) to yield 1.96 g (2.04 μmol) of product 66 (97%) as a colorless oil: IR (CHCl3) 2956, 2929, 2856, 1735, 1613, 1514, 1479, 1448, 1374, 1249, 1174, 1072, 836, 773, 706 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.53 (m, 6H), 7.33 (m, 11H), 6.84 (m, 2H), 5.81 (dd, J=15.7, 6.1 Hz, 1H), 5.65 (m, 1H), 5.45 (m, 2H), 4.65 (m, 1H), 4.56 (d, J=10.9 Hz, 1H), 4.45 (d, J=10.9 Hz, 1H), 4.14 (q, J=7.1 Hz, 2H), 3.96 (m, 1H), 3.80 (s, 3H), 3.62 (m, 2H), 3.14 (m, 1H), 2.79 (m, 1H), 2.43 (m, 1H), 2.23 (m, 1H), 1.72 (m, 2H), 1.54 (m, 3H), 1.28 (t, J=7.1 Hz, 3H), 1.06 (d, J=6.7 Hz, 3H), 1.01 (d, J=6.9 Hz, 3H), 0.97 (s, 18H), 0.93 (d, J=6.4 Hz, 3H), 0.17 (s, 3H), 0.154 (s, 3H), 0.151 (s, 3H), 0.14 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 173.6, 158.8, 144.4, 134.6, 133.6, 132.1, 131.2, 129.1, 128.7, 127.7, 126.8, 126.4, 103.4, 86.6, 86.1, 73.8, 72.8, 66.5, 65.2, 60.0, 55.1, 42.8, 42.3, 35.4, 35.1, 32.3, 29.4, 26.0, 25.9, 18.4, 18.1, 14.6, 14.2, 13.9, −2.9, −4.0, 4.1; HRMS (ESI) calcd for C59H86O7Si2K 1001.5549 (M+K)+, found 1001.5586; [α]20D−9.8 (c 0.95, CHCl3).

Workup

  1. customthe reaction mixture was evaporated
  2. filtrationfiltered with Celite
  3. concentrationThe organic phase was concentrated
  4. customthe residue was purified by flash chromatography (EtOAc/Hexane 1:9)

Sources & evidence

ORD record
ord-4a39b88aab2a4ee18a71a696a81337ae
Source dataset
uspto-grants-2011_06
Patent number
US07968736B2

Reaction notes

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