Dicyclohexylcarbodiimide → HCID 86586326, compound

HRID 368888Notes

Reaction equation

HRID 368888 reaction equation
[C:1]1(CC[C@H](C2C=CC=C(OCCCC(=O)NOC(C)(C)C)C=2)O)[CH:6]=CC=C[CH:2]=1.[O:29]=[C:30]([N:38]1[CH2:43][CH2:42][CH2:41][CH2:40][C@H:39]1[C:44]([OH:46])=[O:45])[C:31](=[O:37])[C:32]([CH3:36])([CH3:35])[CH2:33][CH3:34].C1(N=C=NC2CCCCC2)CCCCC1>C(Cl)Cl.CN(C)C1C=CN=CC=1>[CH3:36][C:32]([CH3:35])([CH2:33][CH3:34])[C:31](=[O:37])[C:30]([N:38]1[CH2:43][CH2:42][CH2:41][CH2:40][C@H:39]1[C:44]([O:46][CH2:2][CH2:1][CH3:6])=[O:45])=[O:29]

Participants

6

Reactant 3

HCID 10868DicyclohexylcarbodiimideHCID 5289328HCID 5289328, compoundHCID 54443070HCID 54443070, compound

Product 1

HCID 86586326HCID 86586326, compoundYield 176.2%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

A solution of alcohol 2 (385 mg, 1.0 mmol) in CH2Cl2 (3 mL) was treated with (2S)-1-(1,2-dioxo-3,3-dimethylpentyl)-2-piperidinecarboxylic acid (23, 255 mg, 1.0 mmol, prepared from L-pipercolic acid in 4 steps following literature procedures by Holt et al. J. Amer. Chem. Soc., 1993, 115, 9925-9938), followed by 1,3-dicyclohexylcarbodiimide (DCC, 247 mg, 1.2 mmol), and 4-(dimethylamino)-pyridine (DMAP, 85 mg, 0.70 mmol) under a nitrogen atmosphere. The resulting bright yellow suspension was allowed to stir overnight. The mixture was then filtered through glass wool and chromatographed (silica gel, 20% EtOAc/hexanes) to give (1R)-3-Phenyl-1-[3-9(3-tert-butyloxycarbamylpropyl)oxy)phenyl]-1-propyl (2S)-1-(3,3-dimethyl-1,2-dioxopentyl)-2-piperidinecarboxylate (524 mg, 84%) as a colorless oil: 1H NMR (CDCl3, 300 MHz) (single diastereomer, mixture of rotamers) 7.35-6.90 (m, 9 H), 5.80 (t, J=5.9 Hz, 1 H), 5.32 (d, J=5.0 Hz, 0.82 H, pipercolate α-H of rotamer A), 4.80 (br. s, 1 H), 4.02 (t, J=6.1 Hz, 2 H), 3.40-3.25 (m, 3 H), 3.12 (td, J=13.0, 3.3 Hz, 1 H), 2.60 (m, 2 H), 2.35 (d, J=14 Hz, 1 H), 2.28 (m, 1 H), 2.07 (m, 1 H), 1.96 (t, J=6.3 Hz, 2 H), 1.80-1.60 (m, 5 H), 1.43 (s, 9 H), 1.22 (s, 3 H), 1.20 (s, 3 H), 0.88 (t, J=7.4 Hz, 3 H); 13C NMR (CDCl3, 75 MHz) (single diastereomer, mixture of rotamers) 208.2, 170.1, 167.6, 159.4, 156.4, 141.7, 141.3, 130.1, 128.9, 128.7, 126.5, 119.4, 114.7, 113.2, 113.0, 66.1, 57.1, 51.7, 47.1, 44.5, 38.3, 32.9, 32.1, 30.0, 28.8, 26.8, 25.4, 24.9, 24.0, 23.8, 23.5, 21.6, 9.1. MS(FAB): (M+Na)+ 645, (M+H)+ 623.

Workup

  1. filtrationThe mixture was then filtered through glass wool
  2. customchromatographed (silica gel, 20% EtOAc/hexanes)

Sources & evidence

ORD record
ord-38e060898a30407aa5a656ae3e167a84
Source dataset
uspto-grants-2000_10
Patent number
US06133456

Reaction notes

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