4,4,5,5-Tetramethyl[1,3,2]dioxaborolane → (3R,4S)-tert-butyl 3-acetamido-3-(tert-butylcarbamoyl)-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl)pyrrolidine-1-carboxylate

HRID 590699

Reaktionsgleichung

Reaktionsgleichung von HRID 590699
[C:1]([NH:4][C@:5]1([C:20](=[O:26])[NH:21][C:22]([CH3:25])([CH3:24])[CH3:23])[C@@H:9]([CH2:10][CH:11]=[CH2:12])[CH2:8][N:7]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:6]1)(=[O:3])[CH3:2].[CH3:27][C:28]1([CH3:35])[C:32]([CH3:34])([CH3:33])[O:31][BH:30][O:29]1>C(Cl)Cl.[Ir].ClC1CCC=CCCC=1.C1(P(C2C=CC=CC=2)CCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:1]([NH:4][C@:5]1([C:20](=[O:26])[NH:21][C:22]([CH3:25])([CH3:24])[CH3:23])[C@@H:9]([CH2:10][CH2:11][CH2:12][B:30]2[O:31][C:32]([CH3:34])([CH3:33])[C:28]([CH3:35])([CH3:27])[O:29]2)[CH2:8][N:7]([C:13]([O:15][C:16]([CH3:17])([CH3:18])[CH3:19])=[O:14])[CH2:6]1)(=[O:3])[CH3:2]

Komponenten

6

Edukt 2

HCID 27347684,4,5,5-Tetramethyl[1,3,2]dioxaborolaneHCID 69669632rel-(3R,4S)-tert-Butyl 3-acetamido-4-allyl-3-(tert-butylcarbamoyl)pyrrolidine-1-carboxylate

Produkt 1

HCID 67517991(3R,4S)-tert-butyl 3-acetamido-3-(tert-butylcarbamoyl)-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl)pyrrolidine-1-carboxylateAusbeute 82,5 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 742671,2-Bis(diphenylphosphino)ethaneKatalysatorHCID 86594784Chloro-1,5-cyclooctadiene iridiumKatalysatorHCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
-20 °C

Versuchsvorschrift

A stirred solution of (3R,4S)-tert-butyl 3-acetamido-4-allyl-3-(tert-butylcarbamoyl)pyrrolidine-1-carboxylate (5.51 g, 15 mmol) in anhydrous methylene chloride (80 mL) under nitrogen was treated with chloro-1,5-cyclooctadiene iridium dimer (0.252 g, 0.375 mmol) and 1,2-bis(diphenylphosphino)ethane (0.299 g, 0.75 mmol), stirred for 30 min, and cooled (−20° C.). 4,4,5,5-Tetramethyl-1,3,2-dioxaborolane (3.30 mL, 22.5 mmol) was added dropwise, and the solution was placed in an ice bath and allowed to reach room temperature overnight (18 h). The mixture was quenched with water (75 mL), stirred 15 min, and extracted with ethyl acetate (400 mL, then 2×100 mL). The combined organic solution was washed with saturated aqueous sodium chloride (150 mL), dried (MgSO4), and concentrated. The solid was recrystallized (2 crops) from acetonitrile to afford (3R,4S)-tert-butyl 3-acetamido-3-(tert-butylcarbamoyl)-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl)pyrrolidine-1-carboxylate (6.13 g, 82%) as a white solid. NMR (CDCl3) δ 6.40-6.60 (m, 1 H), 6.23 (s, 1 H), 3.95-4.05 (m, 1 H), 3.65-3.75 (m, 2 H), 2.90-3.20 (m, 2 H), 2.00 (s, 3 H), 1.45 (s, 9 H), 1.30-1.45 (m, 4 H), 1.33 (s, 9 H), 1.22 (s, 12 H), 0.70-0.80 (m, 2 H). MS (m+1): 496.4.

Aufarbeitung

  1. customthe solution was placed in an ice bath
  2. waitto reach room temperature overnight
  3. custom(18 h)
  4. customThe mixture was quenched with water (75 mL)
  5. stirringstirred 15 min
  6. extractionextracted with ethyl acetate (400 mL
  7. washThe combined organic solution was washed with saturated aqueous sodium chloride (150 mL)
  8. dry with materialdried (MgSO4)
  9. concentrationconcentrated
  10. customThe solid was recrystallized (2 crops) from acetonitrile

Quellen und Nachweise

ORD-Eintrag
ord-c0529111b9e0413fba81ba534427e210
Quelldatensatz
uspto-grants-2016_01
Patentnummer
US09233985B2

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