Oxalyl chloride → HCID 66858870, compound

HRID 2179773Notes

Reaction equation

HRID 2179773 reaction equation
[C:1]([O:4][C@H:5]1[CH2:22][CH2:21][C@@:20]2([CH3:23])[C@@H:7]([CH2:8][CH2:9][C@:10]3([CH3:34])[C@@H:19]2[CH2:18][CH2:17][C@H:16]2[C@@:11]3([CH3:33])[CH2:12][CH2:13][C@@:14]3([C:30](O)=[O:31])[CH2:26][CH2:25][C@@H:24]([C:27]([CH3:29])=[CH2:28])[C@@H:15]32)[C:6]1([CH3:36])[CH3:35])(=[O:3])[CH3:2].C(Cl)(C(Cl)=O)=O.[NH2:43][C@@H:44]1[CH2:47][C@H:46]([C:48]([N:50]2[CH2:55][CH2:54][O:53][CH2:52][CH2:51]2)=[O:49])[C:45]1([CH3:57])[CH3:56]>C(Cl)Cl>[C:1]([O:4][C@H:5]1[CH2:22][CH2:21][C@@:20]2([CH3:23])[C@@H:7]([CH2:8][CH2:9][C@:10]3([CH3:34])[C@@H:19]2[CH2:18][CH2:17][C@H:16]2[C@@:11]3([CH3:33])[CH2:12][CH2:13][C@@:14]3([C:30](=[O:31])[NH:43][C@@H:44]4[CH2:47][C@H:46]([C:48]([N:50]5[CH2:55][CH2:54][O:53][CH2:52][CH2:51]5)=[O:49])[C:45]4([CH3:57])[CH3:56])[CH2:26][CH2:25][C@@H:24]([C:27]([CH3:29])=[CH2:28])[C@@H:15]32)[C:6]1([CH3:36])[CH3:35])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 65578Oxalyl chlorideHCID 1030053410376-50-8HCID 58111022HCID 58111022, compound2×

Product 1

HCID 66858870HCID 66858870, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent4×

Procedure

To a solution of (1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13aR,13bR)-9-acetoxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (0.270 g, 0.542 mmol) in DCM (1 ml) 2M solution of (COCl)2 in DCM (2.71 ml, 5.42 mmol) was added at about 0° C. and the reaction mixture was stirred at room temperature for about 3 hours. After completion of the reaction (monitored by TLC), the solvent was evaporated under nitrogen atmosphere and dissolved in DCM (4 ml), which was added to a solution of ((1S,3R)-3-amino-2,2-dimethylcyclobutyl)(morpholino)methanone (Intermediate 14, 0.172 g, 0.0813 mmol) in DCM at 0° C. and allowed to stir at room temperature for about 16 hours. After completion of the reaction (monitored by TLC), the reaction mixture was diluted with DCM and washed with water, 1N HCl, water, brine and dried over Na2SO4, the solvent was evaporated and purified by silica gel column (100-200 mesh, elution 15% EtOAc in hexane) to afford the title compound as an off white solid. Wt: 0.310 g: Yield: 82%; 1H NMR (300 MHz, CDCl3): δ 5.83 (d, 1H, J=7.8 Hz), 4.72 (s, 1H), 4.58 (s, 1H), 4.51-4.40 (m, 1H), 4.19-4.08 (m, 1H), 3.81-3.40 (m, 8H), 3.18-3.05 (m, 1H), 2.90-2.82 (m, 1H), 2.54-2.21 (m, 3H), 2.04 (s, 3H), 1.99-1.83 (m, 2H), 1.80-1.12 (m, 27H), 1.08-1.70 (s, 18H); Mass: [M+1]+ 693 (15%), [M+Na]+ 715 (28%); JR (KBr, cm−1): 3388, 2954, 2867, 1716, 1659, 1633, 1524, 1449, 1366, 1271, 1235, 1119, 1038, 980, 892; M.R: 71.6° C.-78.9° C.

Workup

  1. customAfter completion of the reaction (monitored by TLC)
  2. customthe solvent was evaporated under nitrogen atmosphere
  3. dissolutiondissolved in DCM (4 ml)
  4. stirringto stir at room temperature for about 16 hours
  5. customAfter completion of the reaction (monitored by TLC)
  6. washwashed with water, 1N HCl, water, brine
  7. dry with materialdried over Na2SO4
  8. customthe solvent was evaporated
  9. custompurified by silica gel column (100-200 mesh, elution 15% EtOAc in hexane)

Sources & evidence

ORD record
ord-b83a66ff6b93487e8eb9b93b76afc757
Source dataset
uspto-grants-2015_06
Patent number
US09067966B2

Reaction notes

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