2-adamantyl Chloroformate → Carbonate Ion

HRID 1198066Notes

Reaction equation

HRID 1198066 reaction equation
[CH3:1][C@:2]([C:14]([NH:16][C@H:17]([CH2:25][OH:26])[CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:15])([CH2:4][C:5]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[NH:7][CH:6]=1)[NH2:3].[CH:27]12[CH2:36][CH:31]3[CH2:32][CH:33]([CH2:35][CH:29]([CH2:30]3)[CH:28]1[O:37][C:38](Cl)=[O:39])[CH2:34]2>C1COCC1.C(OCC)(=O)C>[CH:29]12[CH2:35][CH:33]3[CH2:32][CH:31]([CH2:36][CH:27]([CH2:34]3)[CH:28]1[O:37][C:38](=[O:39])[NH:3][C:2]([CH2:4][C:5]1[C:13]3[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=3)[NH:7][CH:6]=1)([CH3:1])[C:14]([NH:16][CH:17]([CH2:25][OH:26])[CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:15])[CH2:30]2.[C:38](=[O:39])([O-:15])[O-:37]

Participants

6

Reactant 2

HCID 108785372-adamantyl ChloroformateHCID 54471265alpha-methyl-D-tryptophyl-L-phenylalaninol

Product 2

HCID 19660Carbonate IonYield 20%HCID 10165354Tricyclo[3.3,1.13,7]dec-2-yl-[2-[[1-(hydroxymethyl)-2-phenylethyl]amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A solution of the α-methyl-D-tryptophyl-L-phenylalaninol (0.5 g, 1.42 mmol) and 4-N,N-dimethylaminopyridine (0.2 g,1.64 mmol), in anhydrous THF (20 mL) was treated dropwise with a solution of 2-adamantylchloroformate (1.4 mmol) in anhydrous THF (20 mL) at room temperature. The reaction was monitored by IR spectroscopy. Once complete, the reaction mixture was diluted with ethyl acetate and washed with 1M citric acid solution, then water. The dried (MgSO4) organic phase was evaporated to dryness and chromatographed over silica using 2% MeOH:98% CH2Cl2 as eluant. This gave the required compound (65% along with 20% carbonate impurity. NOTE: Some of the more acid labile urethanes required chromatography on neutral stationary phases. mp 96°-100° C. (EtOAc-hexane); IR (KBr) 3316, 1695 and 1658 cm-1 ; NMR (CD3OD) δ 1.28 (3H, s), 1.55 (2H, m), 1.68-2.06 (12H, m), 2.76 (2H, ABx, J 13.5 and 17 Hz), 3.31 (2H, Abq, J 14.5 Hz), 3.45 (2H, m), 4.12 (1H, m), 4.78 (1H, br.s) and 6.8-7.5 (10H, m); Anal. (C32H39N3O4), C, H, N.

Workup

  1. washwashed with 1M citric acid solution
  2. dry with materialThe dried (MgSO4) organic phase
  3. customwas evaporated to dryness
  4. customchromatographed over silica using 2% MeOH

Sources & evidence

ORD record
ord-c128b85cee724710a92c51f4e92f55fe
Source dataset
uspto-grants-1994_01
Patent number
US05278316

Reaction notes

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