Lithium Hydroxide → HCID 23656939, compound

HRID 1012856Notes

Reaction equation

HRID 1012856 reaction equation
C[O:2][C:3](=[O:72])[CH2:4][NH:5][C:6](=[O:71])[C@H:7]([NH:11][C:12](=[O:70])[C@H:13]([NH:35][C:36](=[O:69])[C@H:37]([NH:39][C:40](=[O:68])[CH2:41][C@H:42]([OH:67])/[CH:43]=[CH:44]/[CH2:45][CH2:46][S:47][C:48]([C:61]1[CH:66]=[CH:65][CH:64]=[CH:63][CH:62]=1)([C:55]1[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=1)[C:49]1[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=1)[CH3:38])[CH2:14][S:15][C:16]([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[CH:8]([CH3:10])[CH3:9].[Li+].[OH-].OS([O-])(=O)=O.[K+]>C1COCC1.O>[OH:67][C@H:42](/[CH:43]=[CH:44]/[CH2:45][CH2:46][S:47][C:48]([C:55]1[CH:56]=[CH:57][CH:58]=[CH:59][CH:60]=1)([C:61]1[CH:66]=[CH:65][CH:64]=[CH:63][CH:62]=1)[C:49]1[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=1)[CH2:41][C:40]([NH:39][C@H:37]([CH3:38])[C:36]([NH:35][C@H:13]([CH2:14][S:15][C:16]([C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)([C:23]1[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=1)[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[C:12]([NH:11][C@H:7]([CH:8]([CH3:9])[CH3:10])[C:6]([NH:5][CH2:4][C:3]([OH:72])=[O:2])=[O:71])=[O:70])=[O:69])=[O:68]

Participants

6

Reactant 3

HCID 3939Lithium HydroxideHCID 516920Potassium bisulfateHCID 23656765HCID 23656765, compound

Product 1

HCID 23656939HCID 23656939, compoundYield 99.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of 6A (700 mg, 0.70 mmol) in THF (15 mL) at 0° C. was added a solution of LiOH (25 mg, 1.05 mmol) in H2O (2.4 mL). After stirring for 1 hour, the reaction mixture was diluted with H2O (30 mL), acidified to pH 3-4 with 1M KHSO4, and extracted with EtOAc (3×30 mL). The organic layer was washed with sat NaCl (15 mL), dried (Na2SO4), filtered, and concentrated to give a white solid which was triturated with ether, to give 7A as a white solid (693 mg, 99%) which was used crude directly in the next step. mp=191-193° C.; [α]22D 18.5 (c 0.50, CHCl3); IR νmax 3413, 1711, 1678, 1630, 1451 cm−1; 1H NMR (400 MHz, 5% CD3OD/CDCl3) δ 7.30 (m, 12H), 7.16 (m, 12H), 7.13 (m, 6H), 5.43 (dt, J=15.5 Hz, 6.0 Hz, 1H), 5.30 (dd, J=15.5 Hz, 6.0 Hz, 1H), 4.27 (m, 2H), 4.21 (m, 1H), 3.99 (m, 1H), 3.75 (s, 2H), 3.77 (m, br, 6H), 2.55 (dd, J=12.5 Hz, 6.5 Hz, 1H), 2.44 (dd, J=12.5 Hz, 7.5 Hz, 1H), 2.21 (m, 2H), 2.12 (m, 3H), 2.02 (m, 2H), 1.23 (d, J=7.0 Hz, 3H), 0.83 (d, J=7.0 Hz, 3H), 0.80 (d, J=7.0 Hz, 3H); 13C NMR (100 MHz, 5% CD3OD/CDCl3) δ 173.0, 172.1, 171.6, 171.5, 170.5, 144.9, 144.3, 132.7, 129.8, 129.6, 129.5, 128.2, 127.9, 127.0, 126.7, 69.5, 67.1, 66.7, 58.7, 52.7, 43.5, 40.9, 33.2, 31.5, 31.3, 30.3, 19.2, 19.1, 17.6; LRMS m/z 1013.2 (100%, [M+Na]+).

Workup

  1. extractionextracted with EtOAc (3×30 mL)
  2. washThe organic layer was washed with sat NaCl (15 mL)
  3. dry with materialdried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto give a white solid which
  7. customwas triturated with ether

Sources & evidence

ORD record
ord-c2853890d80849c5bc07e8f98c584f13
Source dataset
uspto-grants-2011_07
Patent number
US07977304B2

Reaction notes

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