Triethylamine → [2-[2-(Tert-butyl-dimethyl-silanyloxymethyl)-pyrrolidine-1-carbonyl]-4,5-dimethoxy-phenyl]-carbamic acid-3-(4-nitrophenyl)-allyl ester

HRID 33991Notes

Reaction equation

HRID 33991 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([CH:10]=[CH:11][CH2:12][OH:13])=[CH:6][CH:5]=1)([O-:3])=[O:2].C(N(CC)CC)C.[C:21]([SiH2:25][O:26][C:27]([CH3:49])([CH3:48])[CH:28]1[CH2:32][CH2:31][CH2:30][N:29]1[C:33]([C:35]1[CH:40]=[C:39]([O:41][CH3:42])[C:38]([O:43][CH3:44])=[CH:37][C:36]=1[N:45]=[C:46]=[O:47])=[O:34])([CH3:24])([CH3:23])[CH3:22].NC1C=C(OC)C(OC)=CC=1C(N1CCCC1C(C)(C)O[SiH2]C(C)(C)C)=O.ClC(Cl)(OC(=O)OC(Cl)(Cl)Cl)Cl>C(Cl)Cl.C1(C)C=CC=CC=1.CCOC(C)=O>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([CH:10]=[CH:11][CH2:12][O:13][C:46](=[O:47])[NH:45][C:36]2[CH:37]=[C:38]([O:43][CH3:44])[C:39]([O:41][CH3:42])=[CH:40][C:35]=2[C:33]([N:29]2[CH2:30][CH2:31][CH2:32][CH:28]2[C:27]([CH3:49])([CH3:48])[O:26][SiH2:25][C:21]([CH3:23])([CH3:22])[CH3:24])=[O:34])=[CH:8][CH:9]=1)([O-:3])=[O:2]

Participants

9

Reactant 5

HCID 8471Triethylamine2×HCID 739253-(4-Nitrophenyl)prop-2-en-1-olHCID 94429TriphosgeneHCID 131727078[2-(tert-Butyl-dimethyl-silanyloxymethyl)-pyrrolidin-1-yl]-(2-isocyanato-4,5-dimethoxy-phenyl)-methanoneHCID 131727079(2-Amino-4,5-dimethoxy-phenyl)-[2-(tert-butyl-dimethyl-silanyloxymethyl)-pyrrolidin-1-yl]-methanone

Product 1

HCID 131727080[2-[2-(Tert-butyl-dimethyl-silanyloxymethyl)-pyrrolidine-1-carbonyl]-4,5-dimethoxy-phenyl]-carbamic acid-3-(4-nitrophenyl)-allyl ester

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 3-(4-nitrophenyl)-prop-2-en-1-ol (0.222 g, 1.24 mmol) and triethylamine (0.138 g, 0.19 mL, 1.37 mmol) in anhydrous CH2Cl2 (10 mL) was added to a solution of the isocyanate 7 prepared from the amine 5 (0.491 g, 1.24 mmol), triphosgene (0.132 g, 0.45 mmol) and triethylamine (0.17 g, 0.23 mL, 1.68 mmol) in anhydrous toluene (20 mL). The reaction was complete in 20 hours. The product was obtained (flash column chromatography 50% EtOAc/50% n-hexane) as a yellow oil which crystallised (0.432 g, 58%): νmax/cm−1 (film) (C=0, carbamate); [α]D25.3−65.0° (c=0.24, CHCl3), 1H NMR (CDCl3) δ 9.39 (bs, 1H), 7.89 ((s, 1H), 8.19 (d, J=8.8 Hz, 2H), 7.53 (d, J=9 Hz, 2H), 6.85 (s, 1H), 6.73 (d, J=15.9 Hz, 1H), 6.52 (dt, J=5.8, 15.9 Hz, 1H) 4.86 (m, 2H) 4.38 (m, 1H), 4.01 (m, 1H), 3.94 (s, 3H), 3.83 (s, 3H), 3.70 (m, 1H), 3.52 (m, 2H), 2.06 (m, 2H), 1.95 (m, 1H), 1.72 (m, 1H), 0.9 (s, 9H), 0.08 (s, 6H). IR (neat) 3340, 2930, 1729, 1597, 1519 cm−1. HRMS m/z calcd for C30H31N3O8SiNa 622.2561 (M+Na), found 622.2542.

Workup

  1. customcrystallised (0.432 g, 58%)

Sources & evidence

ORD record
ord-00aed324f4474490902c17bf39d22d9b
Source dataset
uspto-grants-2008_09
Patent number
US07429658B2

Reaction notes

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