Oxygen → HCID 20638842, compound

HRID 1276564Notes

Reaction equation

O=O.C1(S)C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[C:29]([O:37][C@H:38]1[C@:45]([CH3:47])([OH:46])[C@@H:44]2[CH2:48][C@@H:40]([C@@:41]([CH3:57])([CH2:49][S:50][C:51]3[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=3)[O:42][O:43]2)[CH2:39]1)(=[O:36])[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>CCCCCC.C1C=CC=CC=1.CCCCCC>[C:29]([O:37][C@H:38]1[C@@:45]([CH3:47])([OH:46])[C@@H:44]2[CH2:48][C@@H:40]([C@:41]([CH3:57])([CH2:49][S:50][C:51]3[CH:52]=[CH:53][CH:54]=[CH:55][CH:56]=3)[O:42][O:43]2)[CH2:39]1)(=[O:36])[C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1

Participants

Conditions

Temperature: 4 °C

Procedure

Oxygen was bubbled through a solution of the α-benzoate 3b (690 mg, 2.70 mmol) and DBPO (8.5 mg, 0.036 mmol) in hexane-benzene (50 mL, 7:3) with simultaneous addition (syringe pump) of a solution of PhSH (99 mg, 2.0 mmol) in hexane (20 mL) during 10 h. After completion of the thiol addition, the mixture was kept under oxygen for an additional 14 h, cooled to 4° C., and Ph3P (236 mg, 0.90 mmol) was added. The reaction mixture was stirred for 2 h at 5° C. and at rt for additional 1 h. The solvents were then evaporated, and flash chromatography (hexane-EtOAc, 9:1→1:1) afforded a mixture of diastereomeric (1S,4S,5S,7R,8S)-7-benzoyloxy-4,8-dimethyl-4-phenylthiomethyl-2,3-dioxabicyclo[3.3.1]nonan-8-ol 6a and (1S,4R,5S,7R,8R)-7-benzoyloxy-4,8-dimethyl-4-phenylthiomethyl-2,3-dioxabicyclo[3.3.1]nonan-8-ol 6b (24 mg of ca. 94% purity, 6% yield, 6a/6b ca. 65:35), Rf 0.42 (EtOAc-heaxane, 35:65) as a pale yellow oil. 1H NMR (400 ) MHz, CDCl3, δ): 1.23 (br. s, Me11, 6a), 1.59 (br. s, Me11, 6b), total 3 H; 1.41 (s, Me10, 6b), 1.42 (s, Me10, 6a), total 3 H; 1.91-2.37 (m, total 5 H, H35 +Ha,e6 +Ha,e9, 6a+6b); 3.00 (d, 2J=12.1 Hz, H12, 6b), 3.14 (br. d, 2J=12.1 Hz, H'12, 6b), 3.39 (d, 2J=12.8 Hz, H12, 6a), 3.80 (br. d, 2J=12.8 Hz, H'12, 6a), total 2 H; 3.82 (m, He1, 6a), 3.88 (dd, 3J1e9e =4.1 Hz, 3J1e9a =1.5 Hz, He1, 6b), total 1 H; 5.26 (dd, 1 H, 3J7e6e =5.0 Hz, 3J7e6a =1.7 Hz, He7, 6b), 5.27 (dd, 1 H, 1J7e6e =5.0 Hz, 3J7e6a =1.5 Hz, He7, 6a), total 1 H; 7.09 (m, 1 H), 7.22 (m, 6 b), 7.29 (m, 6a), total 2 H; 7.41-7.47 (m,), 7.54-7.58 (m,), total 5 H; 8.13 (m, 2 H), 13C NMR (100 MHz, CDCl3, δ): Isomer 6a: 22.30 (Me11), 23.42 (C9H2), 23.47 (Me10), 28.81 (C6H2), 29.36 (C5H), 40.78 (C12H2), 73.83 (C8), 74.36 (C7H), 80.85 (C1H), 82.74 (C4), 126.36 (C16H), 128.48 (2CH), 129.00 (2CH), 129.81 (2CH), 129.90 (2CH), 130.15 (C1-benz.), 133.11 (Cp-benz. H), 136.71 (C13), 166.33 (C=O); Isomer 6b: 21.68 (Me11), 23.35 (Me10), 23.56 (C9H2), 28.68 (C6H2), 30.86 (C5H), 40.37 (C12H2), 73.68 (C8), 74.51 (C7H), 81.38 (C1H), 82,83 (C4), 126.12 (C16H), 128.52 (2CH), 128.88 (2CH), 129.06 (2CH), 129.81 (C1-benz.), 129.90 (2CH), 133.18 (Cp-benz. H), 136.25 (C13), 166.25 (C=O).

Workup

customThe solvents were then evaporated
customflash chromatography (hexane-EtOAc, 9:1→1:1) afforded

Sources & evidence

ORD record: ord-3c3c1d02fac947278a326042943667fe
Source dataset: uspto-grants-2000_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06166065

Reaction notes

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