Phosphorus pentachloride → HCID 57695537, compound

HRID 2079862Notes

Reaction equation

HRID 2079862 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([NH:14][C:15]([C:17]2[CH:18]=[C:19]([C:39]3[CH:44]=[C:43]([CH:45]([CH3:47])[CH3:46])[CH:42]=[CH:41][C:40]=3[O:48][CH3:49])[C:20]([O:31][CH2:32][C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)=[CH:21][C:22]=2[O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=O)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].P(Cl)(Cl)(Cl)(Cl)Cl.[Si]([N:60]=[N+:61]=[N-:62])(C)(C)C>ClCCl>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([N:14]2[C:15]([C:17]3[CH:18]=[C:19]([C:39]4[CH:44]=[C:43]([CH:45]([CH3:47])[CH3:46])[CH:42]=[CH:41][C:40]=4[O:48][CH3:49])[C:20]([O:31][CH2:32][C:33]4[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=4)=[CH:21][C:22]=3[O:23][CH2:24][C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)=[N:62][N:61]=[N:60]2)[CH2:10][CH2:9]1)=[O:7])([CH3:3])([CH3:4])[CH3:2]

Participants

5

Reactant 3

HCID 24819Phosphorus pentachlorideHCID 78378AzidotrimethylsilaneHCID 57695553HCID 57695553, compound

Product 1

HCID 57695537HCID 57695537, compoundYield 59%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 4-[(4,6-bis-benzyloxy-5′isopropyl-2′methoxy-biphenyl-3-carbonyl)-amino]-piperidine-1-carboxylic acid tert-butyl ester (6.1 g, 9.2 mmol), PCl5 (2.9 g, 13.8 mmol) and anhydrous dichloromethane (120 ml) was stirred at rt for 4 h. Then the TMSN3 (10.4 ml, 1.7 vols.) was charged and the mixture stirred for a further 7 h. The reaction was quenched very carefully with saturated NaHCO3 solution (100 ml) and stirred a further 1 h. The organics were then split off and aqueous washed with dichloromethane. The combined organics were then washed with brine before being dried (Na2SO4), filtered and evaporated to yield the crude product as a yellow solid. This material was purified using column flash chromatography (SiO2, ethyl acetate/hexanes), yielding 4-[5-(4,6-bis-benzyloxy-5′-isopropyl-2′-methoxy-biphenyl-3-yl)-tetrazol-1-yl]-piperidine-1-carboxylic acid tert-butyl ester as a white solid (3.7 g, 59%). M.p.: 77-81° C.; 400 MHz 1H NMR (DMSO-d) δ: 7.45-7.09 (m, 14H), 6.96 (d, J=6.4 Hz, 1H), 5.26 (s, 2H), 5.23 (s, 2H), 4.45 (br s, 1H), 3.86 (m, 2H), 3.67 (s, 3H), 2.84 (m, 3H), 1.67 (m, 4H), 1.40 (s, 9H), 1.16 (d, J=6.4 Hz, 6H); LCMS: 690 [M+H].

Workup

  1. customThe reaction was quenched very carefully with saturated NaHCO3 solution (100 ml)
  2. stirringstirred a further 1 h
  3. customThe organics were then split off
  4. washaqueous washed with dichloromethane
  5. washThe combined organics were then washed with brine
  6. dry with materialbefore being dried (Na2SO4)
  7. filtrationfiltered
  8. customevaporated
  9. customto yield the crude product as a yellow solid
  10. customThis material was purified

Sources & evidence

ORD record
ord-dd15241c3aed42aba55bc95d1bb122e9
Source dataset
uspto-grants-2011_04
Patent number
US07932279B2

Reaction notes

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