Sodium Carbonate Monohydrate → HCID 86692321, compound

HRID 1400975Notes

Reaction equation

FC(F)(F)S(O[C:7]1[C:8]([CH3:36])([CH3:35])[C@H:9]2[C@:22]([CH3:25])([CH2:23][CH:24]=1)[C@@H:21]1[C@:12]([CH3:34])([C@@:13]3([CH3:33])[C@H:18]([CH2:19][CH2:20]1)[C@H:17]1[C@H:26]([C:29]([CH3:31])=[CH2:30])[CH2:27][CH2:28][C@:16]1([NH2:32])[CH2:15][CH2:14]3)[CH2:11][CH2:10]2)(=O)=O.CC1(C)C(C)(C)OB([C:47]2[CH2:52][CH2:51][CH:50]([C:53]([O:55][CH3:56])=[O:54])[CH2:49][CH:48]=2)O1.O.C(=O)([O-])[O-].[Na+].[Na+]>O1CCOCC1.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:32][C@:16]12[CH2:28][CH2:27][C@@H:26]([C:29]([CH3:31])=[CH2:30])[C@@H:17]1[C@@H:18]1[C@@:13]([CH3:33])([CH2:14][CH2:15]2)[C@@:12]2([CH3:34])[C@@H:21]([C@:22]3([CH3:25])[C@@H:9]([CH2:10][CH2:11]2)[C:8]([CH3:35])([CH3:36])[C:7]([C:47]2[CH2:52][CH2:51][CH:50]([C:53]([O:55][CH3:56])=[O:54])[CH2:49][CH:48]=2)=[CH:24][CH2:23]3)[CH2:20][CH2:19]1

Participants

Conditions

Temperature: 85 °C

Procedure

To a sealable vial containing (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl trifluoromethanesulfonate (0.109 g, 0.195 mmol) was added methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohex-3-enecarboxylate (0.078 g, 0.293 mmol), sodium carbonate hydrate (0.073 g, 0.586 mmol), and tetrakis(triphenylphosphine)palladium(0) (6.77 mg, 5.86 mmol). The mixture was diluted with 1,4-dioxane (2 mL) and water (0.5 mL) then was flushed with nitrogen, sealed and heated to 85° C. in an oil bath. After 20.5 h, the mixture was cooled to rt, diluted with water (10 mL) and extracted with dichloromethane (3×10 mL). The combined organic layers were dried with sodium sulfate. The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was adsorbed to silica gel and purified by chromatography using a 12 g Thomson silica gel column and a 10%-80% ethyl acetate in hexanes gradient. The fractions containing the expected product were combined and concentrated under reduced pressure to give methyl 4-((1R,3 aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)cyclohex-3-enecarboxylate (0.035 g, 0.064 mmol, 32.7% yield) as an off-white solid. 1H NMR (400 MHz, chloroform-d) δ=5.35 (br. s., 1H), 5.19 (d, J=5.8 Hz, 1H), 4.73 (s, 1H), 4.60 (br. s., 1H), 3.69 (s, 3H), 2.55 (td, J=10.7, 5.1 Hz, 2H), 2.31 (d, J=2.3 Hz, 2H), 2.22-1.94 (m, 6H), 1.70 (s, 3H), 1.07 (s, 3H), 1.79-0.81 (m, 34H).

Workup

customthen was flushed with nitrogen
customsealed
temperaturethe mixture was cooled to rt
additiondiluted with water (10 mL)
extractionextracted with dichloromethane (3×10 mL)
dry with materialThe combined organic layers were dried with sodium sulfate
customThe drying agent was removed by filtration
concentrationthe filtrate was concentrated under reduced pressure
custompurified by chromatography
additionThe fractions containing the expected product
concentrationconcentrated under reduced pressure

Sources & evidence

ORD record: ord-8284a947880a4b54b87b73439121bb00
Source dataset: uspto-grants-2014_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08906889B2

Reaction notes

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