Ethyl Acetate → Benzyl 3-(6-{3-[(tert-butoxycarbonyl)amino]prop-1-ynyl}pyridin-3-yl)prop-2-ynylcarbamate

HRID 49571

Reaction equation

HRID 49571 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5](Br)=[CH:4][N:3]=1.[C:9]([NH:16][CH2:17][C:18]#[CH:19])([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10].[C:20]([NH:30][CH2:31][C:32]#[CH:33])([O:22][CH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)=[O:21].C(OCC)(=O)C>C(NC(C)C)(C)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[C:12]([O:11][C:9]([NH:16][CH2:17][C:18]#[C:19][C:2]1[N:3]=[CH:4][C:5]([C:33]#[C:32][CH2:31][NH:30][C:20](=[O:21])[O:22][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)=[CH:6][CH:7]=1)=[O:10])([CH3:13])([CH3:14])[CH3:15]

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 693532,5-DibromopyridineHCID 11073648tert-butyl N-(prop-2-yn-1-yl)carbamateHCID 11137906Benzyl prop-2-yn-1-ylcarbamate

Product 1

HCID 21299383Benzyl 3-(6-{3-[(tert-butoxycarbonyl)amino]prop-1-ynyl}pyridin-3-yl)prop-2-ynylcarbamateYield 11.9%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 7912DiisopropylamineSolvent

Procedure

A mixture of 2,5-dibromopyridine (1.19 g), N-Boc-propargylamine (781 mg), Pd(PPh3)2Cl2 (73 mg), and CuI (10 mg) in diisopropylamine (20 mL) was stirred at room temperature overnight under nitrogen atmosphere. To the mixture was added N-Cbz-propargylamine (1.14 g) and the mixture was heated under reflux temperature for 5 hours under nitrogen atmosphere. The mixture was cooled to room temperature. To the mixture was added ethyl acetate (50 mL). The precipitates were filtered and washed with ethyl acetate. The filtrate and washings were combined and purified by silica gel column to give 6-1 (250 mg) as a crystalline compound.

Workup

  1. temperaturethe mixture was heated
  2. temperatureunder reflux temperature for 5 hours under nitrogen atmosphere
  3. temperatureThe mixture was cooled to room temperature
  4. filtrationThe precipitates were filtered
  5. washwashed with ethyl acetate
  6. custompurified by silica gel column

Sources & evidence

ORD record
ord-23e7eb85123f438d84ad90e4f736190c
Source dataset
uspto-grants-2004_03
Patent number
US06706885B2

Linked notes

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