Pyridine → HCID 91202774, compound

HRID 628183Notes

Reaction equation

HRID 628183 reaction equation
[C:1]([O:8][C@@H:9]1[C@@H:17]([O:18][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C@@H:16](O)[C@@H:15]([CH3:27])[O:14][C@@H:10]1[S:11][CH2:12][CH3:13])(=[O:7])[CH2:2][CH2:3][C:4]([CH3:6])=[O:5].N1C=CC=CC=1.FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.[O-]S(C(F)(F)F)(=O)=O.[N-:57]=[N+:58]=[N-:59].[Na+]>C(Cl)Cl.CN(C=O)C>[N:57]([C@@H:16]1[C@@H:15]([CH3:27])[O:14][C@H:10]([S:11][CH2:12][CH3:13])[C@H:9]([O:8][C:1](=[O:7])[CH2:2][CH2:3][C:4]([CH3:6])=[O:5])[C@H:17]1[O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)=[N+:58]=[N-:59]

Participants

8

Reactant 5

HCID 1049PyridineHCID 33557Sodium AzideHCID 67749Trifluoromethanesulfonic anhydrideHCID 2758875TrifluoromethanesulfonateHCID 67420024HCID 67420024, compound

Product 1

HCID 91202774HCID 91202774, compoundYield 79.1%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Procedure

Treatment of 12 (0.50 g, 1.26 mmol) in pyridine (1.02 mL, 12.61 mmol) and DCM (6.5 mL) with trifluoromethanesulfonic anhydride (0.32 mL, 1.90 mmol) followed by treatment of triflate residue in DMF (16 mL) with sodium azide (0.41 g, 6.31 mmol) according to the general procedure for introduction of the C-4 azide group gave compound 13 as colorless oil (0.42 g, 79%). Rf=0.32 (Hexane/EtOAc, 4:1, v:v). [α]27D=+13.1 (CHCl3, c=5.1 mg/mL). 1H NMR (300 MHz, CDCl3): δ 1.67 (t, 3H, J=7.5 Hz, SCH2CH3), 1.30 (d, 3H, J5,6=5.7 Hz, H-6), 2.10 (s, 3H, CH3C(O)CH2CH2C(O)O), 2.44-2.49 (m, 2H, CH3C(O)CH2CH2C(O)O), 2.57-2.67 (m, 4H, SCH2CH3, CH3C(O)CH2CH2C(O)O), 3.11-3.24 (m, 2H, H-4, H-5), 3.48 (t, J3,4=9.0, J2,3=9.0 Hz, H-3), 4.27 (d, 1H, J1,2=9.9 Hz, H-1), 4.68 (d, 1H, J=11.1 Hz, PhCH2), 4.71 (d, 1H, J=11.1 Hz, PhCH′2), 4.94 (dd, 1H, J1,2=9.9, J2,3=9.0 Hz, H-2), 7.22-7.29 (m, 5H, Harom); 13C NMR (75 MHz, CDCl3): δ 14.8 (SCH2CH3), 18.7 (C-6), 23.9 (SCH2CH3), 28.0 (CH3C(O)CH2CH2C(O)O), 29.8 (CH3C(O)CH2CH2C(O)O), 37.8 (CH3C(O)CH2CH2C(O)O), 67.7 (C-4), 72.2 (C-2), 74.9 (PhCH2), 75.1 (C-5), 82.3 (C-3), 83.2 (C-1), [127.9, 128.0, 128.2, 128.4, 137.5 (Carom)], 171.5 (CH3C(O)CH2CH2C(O)O), 206.1 (CH3C(O)CH2CH2C(O)O); MALDI-TOF/MS: m/z: found [M+Na]+ 444.1, C20H27N3O5S calcd for [M+Na]+ 444.15.

Sources & evidence

ORD record
ord-ef47f04c0c734ae88fb1a65f42f6c089
Source dataset
uspto-grants-2016_04
Patent number
US09310366B2

Reaction notes

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