18-Crown-6 → HCID 87767551, compound

HRID 2252493Notes

Reaction equation

HRID 2252493 reaction equation
COC1C=CC(CO[C@@H:9]([C@@H:66]([CH3:71])/[CH:67]=[CH:68]\[CH:69]=[CH2:70])[C@@H:10]([CH3:65])[C@@H:11]([O:57][Si:58]([C:61]([CH3:64])([CH3:63])[CH3:62])([CH3:60])[CH3:59])[CH2:12][CH2:13][C@H:14]([CH3:56])[CH2:15][C@H:16]([CH3:55])[C@@H:17]([O:47][Si:48]([C:51]([CH3:54])([CH3:53])[CH3:52])([CH3:50])[CH3:49])[C@@H:18]([CH3:46])/[CH:19]=[CH:20]\[C@@H:21]([O:38][Si:39]([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:41])[CH3:40])[CH2:22][C@H:23]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[C@H:24]([CH3:29])/[CH:25]=[CH:26]/CO)=CC=1.CC(OI1(OC(C)=O)(OC(C)=O)[O:87][C:85](=O)[C:84]2[CH:83]=[CH:82][CH:81]=[CH:80][C:79]1=2)=O.P([O-])([O-])(O[C:99]([CH2:109]C(F)(F)F)(CC(F)(F)F)[C:100]([O:102][CH3:103])=[O:101])=O.C1OCCOCCOCCOCCOCC[O:118][CH2:117]1.C[Si]([N-][Si](C)(C)C)(C)C.[K+]>C(Cl)(Cl)Cl.CCOC(C)=O.CCCCCC>[CH3:103][O:102][C:100](=[O:101])/[CH:99]=[CH:109]\[CH:26]=[CH:25]\[C@@H:24]([CH3:29])[C@@H:23]([O:30][Si:31]([C:34]([CH3:36])([CH3:37])[CH3:35])([CH3:32])[CH3:33])[CH2:22][C@H:21]([O:38][Si:39]([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:41])[CH3:40])/[CH:20]=[CH:19]\[C@H:18]([CH3:46])[C@H:17]([O:47][Si:48]([C:51]([CH3:54])([CH3:52])[CH3:53])([CH3:50])[CH3:49])[C@@H:16]([CH3:55])[CH2:15][C@@H:14]([CH3:56])[CH2:13][CH2:12][C@H:11]([O:57][Si:58]([C:61]([CH3:62])([CH3:64])[CH3:63])([CH3:60])[CH3:59])[C@H:10]([CH3:65])[C@@H:9]([O:87][CH2:85][C:84]1[CH:79]=[CH:80][C:81]([O:118][CH3:117])=[CH:82][CH:83]=1)[C@@H:66]([CH3:71])/[CH:67]=[CH:68]\[CH:69]=[CH2:70]

Participants

8

Reactant 5

HCID 2855718-Crown-6HCID 159087TriacetoxyperiodinaneHCID 3251421Potassium bis(trimethylsilyl)amideHCID 87736970HCID 87736970, compoundHCID 131726745HCID 131726745, compound

Product 1

HCID 87767551HCID 87767551, compound

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolvent2×HCID 21226206Ethyl acetate hexaneSolvent

Procedure

The procedure for 46 was used with 54 (117 mg, 0.108 μmol) and Dess-Martin periodinane (69 mg, 0.16 μmol), bis(2,2,2-trifluoroethyl)-(methoxycarbonylmethyl) phosphate (0.027 mL, 0.13 μmol), 18-crown-6 (0.14 g, 0.53 mmol) and KHMDS (0.26 mL, 0.13 μmol, 0.5 M solution in toluene) to yield 69 mg (56% for 2 steps) of the product after flash column chromatography (EtOAc/hexane 1:19) as a colorless oil: IR (CHCl3) 2956, 2929, 2856, 1722, 1640, 1514, 1471, 1462, 1250, 1174, 1080, 836, 773 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.44 (dd, J=15.2, 11.3 Hz, 1H), 7.28 (m, 2H), 6.88 (m, 2H), 6.60 (ddd, J=16.7, 10.6, 10.5 Hz, 1H), 6.56 (t, J=11.3 Hz, 1H), 6.04 (dd, J=15.5, 7.1 Hz, 1H), 6.00 (t, J=11.0 Hz, 1H), 5.62 (m, 2H), 5.42 (m, 1H), 5.27 (m, 1H), 5.21 (d, J=16.8 Hz, 1H), 5.11 (d, J=10.3 Hz, 1H), 4.54 (m, 3H), 3.97 (m, 1H), 3.81 (s, 3H), 3.74 (s, 3H), 3.60 (m, 1H), 3.40 (m, 1H), 3.29 (m, 1H), 2.86 (m, 1H), 2.57 (m, 2H), 1.80-1.67 (m, 3H), 1.55-1.41 (m, 4H), 1.40-1.20 (m, 4H), 1.09 (d, J=6.8 Hz, 3H), 1.06 (d, J=6.8 Hz, 3H), 0.99 (d, J=6.6 Hz, 3H), 0.98 (d, J=6.7 Hz, 3H), 0.95-0.85 (m, 42H), 0.13-0.00 (m, 24H); 13C NMR (75 MHz, CDCl3) δ 166.8, 159.0, 147.3, 145.5, 134.7, 132.9, 132.7, 132.3, 131.4, 129.1, 129.0, 126.9, 117.4, 115.5, 113.7, 84.6, 80.0, 74.7, 73.6, 72.1, 66.5, 55.3, 51.0, 43.5, 42.4, 41.6, 36.1, 35.8, 34.8, 31.9, 30.7, 29.8, 26.3, 26.0, 25.9, 20.5, 19.3, 18.6, 18.5, 18.1, 15.3, 13.4, 10.5, −3.0, −3.3, −3.7, −4.10, −4.15, −4.19, −4.3, −4.4; LRMS (ESI) 1163.8 [M+Na]+, 1057.7, 782.4, 541.1; HRMS (ESI) calcd for C65H120O8Si4Na 1163.7958[M+Na]+, found 1163.8000; [α]20D −16.7 (c 0.33, CHCl3).

Sources & evidence

ORD record
ord-77468d91ebc74078bd7307ef22486dcf
Source dataset
uspto-grants-2008_01
Patent number
US07321046B2

Reaction notes

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