Dichloromethane → HCID 86635875, compound

HRID 1698445Notes

Reaction equation

HRID 1698445 reaction equation
[C:1]([NH:11][C@@H:12]([CH2:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)[C@H:13]([OH:29])[CH2:14][N:15]([CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:16](=[O:21])[CH2:17][C:18](=[O:20])[CH3:19])([O:3][CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:2].S([N:47]=[N+:48]=[N-])(C1C=CC(C)=CC=1)(=O)=O.C1CCN2C(=NCCC2)CC1.ClCCl>C(#N)C>[C:1]([NH:11][C@@H:12]([CH2:30][C:31]1[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=1)[C@H:13]([OH:29])[CH2:14][N:15]([CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:16](=[O:21])[C:17](=[N+:47]=[N-:48])[C:18](=[O:20])[CH3:19])([O:3][CH2:4][C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1)=[O:2]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 13661p-Toluenesulfonyl azideHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 44464416HCID 44464416, compound

Product 1

HCID 86635875HCID 86635875, compoundYield 78%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
0 °C

Procedure

The keto amide (XI) (0.040 g, 0.08 mmol) was dissolved in 0.5 ml of acetonitrile and cooled to 0° C. To this tosyl azide (0.024 g, 0.12 mmol) was added followed by the addition of DBU (18 μL, 0.12 mmol) dropwise. The reaction mixture was stirred for 1 hr at 0° C. and then 3 hrs at room temperature. It was then concentrated under reduced pressure to give dark red oil. The residue was taken up in a minimum volume of dichloromethane and placed on a silica gel column. The compound was eluted with 2:1 hexane/ethyl acetate to give the diazo keto-amide (XII) as yellow oil. 0.033 g (78% yield). 1H NMR (500 MHz, CDCl3) δ 7.13-7.49 (m, 15H), 5.02-5.37 (m, 3H), 4.46-4.87 (m, 2H), 3.75-4.06 (m, 2H), 3.28-3.51 (m, 1H), 2.75-2.94 (m, 2H), 2.05 (s, 3H). 13CNMR (125 MHz, CDCl3) 171, 165.4, 155.85, 140.91, 140.36, 139.22, 129.14, 128.68, 128.26, 128.17, 128.10, 127.72, 127.41, 127.64, 126.75, 79.23, 60.38, 53.14, 50.15, 47.99, 45.6, 37.43, 26.6.

Workup

  1. custom3 hrs
  2. customat room temperature
  3. concentrationIt was then concentrated under reduced pressure
  4. customto give dark red oil
  5. washThe compound was eluted with 2:1 hexane/ethyl acetate

Sources & evidence

ORD record
ord-a87b9653dd1049d2ac036974ea7b5db5
Source dataset
uspto-grants-2012_04
Patent number
US08163953B2

Reaction notes

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