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Water → 7-Demethoxy-7-oxorapamycin

HRID 2147
Notes
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Reaction equation

HRID 2147 reaction equation
[CH3:1][C@H:2]1[C@@:41]2([OH:43])[O:42][C@H:5]([CH2:6][C@H:7]([O:64]C)[C:8]([CH3:63])=[CH:9][CH:10]=[CH:11][CH:12]=[CH:13][C@@H:14]([CH3:62])[CH2:15][C@@H:16]([CH3:61])[C:17]([C@H:19]([O:59][CH3:60])[C@H:20]([OH:58])[C:21]([CH3:57])=[CH:22][C@@H:23]([CH3:56])[C:24]([CH2:26][C@@H:27]([C@@H:44]([CH2:46][C@H:47]3[CH2:52][C@@H:51]([O:53][CH3:54])[C@H:50]([OH:55])[CH2:49][CH2:48]3)[CH3:45])[O:28][C:29]([C@H:31]3[N:36]([C:37]([C:39]2=[O:40])=[O:38])[CH2:35][CH2:34][CH2:33][CH2:32]3)=[O:30])=[O:25])=[O:18])[CH2:4][CH2:3]1.O.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>ClCCl>[CH3:1][C@H:2]1[C@@:41]2([OH:43])[O:42][C@H:5]([CH2:6][C:7]([C:8]([CH3:63])=[CH:9][CH:10]=[CH:11][CH:12]=[CH:13][C@@H:14]([CH3:62])[CH2:15][C@@H:16]([CH3:61])[C:17]([C@H:19]([O:59][CH3:60])[C@H:20]([OH:58])[C:21]([CH3:57])=[CH:22][C@@H:23]([CH3:56])[C:24]([CH2:26][C@@H:27]([C@@H:44]([CH2:46][C@H:47]3[CH2:52][C@@H:51]([O:53][CH3:54])[C@H:50]([OH:55])[CH2:49][CH2:48]3)[CH3:45])[O:28][C:29]([C@H:31]3[N:36]([C:37]([C:39]2=[O:40])=[O:38])[CH2:35][CH2:34][CH2:33][CH2:32]3)=[O:30])=[O:25])=[O:18])=[O:64])[CH2:4][CH2:3]1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 962WaterHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 5284616Sirolimus

Product 1

HCID 1016807387-Demethoxy-7-oxorapamycin

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of rapamycin (5 mg, 0.055 mmol) in dichloromethane (0.1 mL) was added water (0.02 mL) followed by DDQ (2.4 mg, 0.011 mmol), and the resulting dark brown suspension was stirred at room temperature for 45 min. The mixture was filtered through celite and then partitioned between dichloromethane and brine; the organic extracts were dried over anhydrous magnesium sulfate and the resulting crude material was purified by prep TLC. The desired product was isolated as a colorless oil (1.2 mg). 1 H NMR (CDCl3, 400 MHz, 3:1 mixture of trans:cis amide rotamers; data for the trans-rotamer): -- 7.145 (d, J=10.4 Hz, 1H), 6.635 (dd, J=14.9, 10.6 Hz, 1H), 6.57-6.48 (m, 2H), 6.224 (dd, J=15.1, 10.6 Hz, 1H), 5.662 (dd, J=15.1, 8.6 Hz, 1H), 5.447 (d, J=11.2 Hz, 1H), 4.305 (br d, J=5.4 Hz, 1H), 3.983 (d, J=5.4 Hz, 1H), 3.385 (s, 3H), 3.346 (s, 3H),; MS (ESl+/NH4OAc) m/z 920 (M+Na+), 915 (M+NH4+), 898, 880; UV (MeOH) max 318 nm.

Workup

  1. filtrationThe mixture was filtered through celite
  2. custompartitioned between dichloromethane and brine
  3. dry with materialthe organic extracts were dried over anhydrous magnesium sulfate
  4. customthe resulting crude material was purified by prep TLC

Sources & evidence

ORD record
ord-ff129fa8213d45ca8f4648e29b01c951
Source dataset
uspto-grants-1998_03
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05728710

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes