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CAS No. : | 29681-57-0 | MDL No. : | MFCD00010754 |
Formula : | C6H16Si | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | ILMRJRBKQSSXGY-UHFFFAOYSA-N |
M.W : | 116.28 | Pubchem ID : | 9898815 |
Synonyms : |
|
Num. heavy atoms : | 7 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 1.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 39.16 |
TPSA : | 0.0 Ų |
GI absorption : | Low |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.78 cm/s |
Log Po/w (iLOGP) : | 2.52 |
Log Po/w (XLOGP3) : | 3.14 |
Log Po/w (WLOGP) : | 2.27 |
Log Po/w (MLOGP) : | 2.6 |
Log Po/w (SILICOS-IT) : | 0.18 |
Consensus Log Po/w : | 2.14 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.47 |
Solubility : | 0.391 mg/ml ; 0.00336 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.81 |
Solubility : | 0.18 mg/ml ; 0.00155 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -1.91 |
Solubility : | 1.42 mg/ml ; 0.0122 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.55 |
Signal Word: | Danger | Class: | 3 |
Precautionary Statements: | P210-P261-P305+P351+P338 | UN#: | 1993 |
Hazard Statements: | H225-H315-H319-H335 | Packing Group: | Ⅱ |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With 1H-imidazole In dichloromethane at 20℃; for 0.166667 h; Cooling with ice | 3-Bromopropanol (4.14 g, 30 mmol),Was added to DCM (50 mL), imidazole (2.5 g, 30 mmol) was added, stirred under ice for 10 min, TBDMS (4.5 g, 30 mmol) was added and the reaction was continued at room temperature. The next day, DCM (50 mL) (30 mL X3), dried over anhydrous magnesium sulfate and concentrated to give 7 g of a colorless oil in 92percent yield |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With triethylamine In dichloromethane for 8h; Ambient temperature; | |
100% | With palladium diacetate; triethylamine In dichloromethane for 8h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With sodium hydroxide; In tetrahydrofuran; N,N-dimethyl-formamide; at 65℃; for 24.0h;Inert atmosphere; Sealed tube; | General procedure: NaOH (0.05 mmol, 10 mol %) was added to a hot, oven-dried 2 dram scintillation vial equipped with a magnetic stirring bar, and the vial was purged with argon until cool. Alcohol (0.5 mmol, 1 equiv) was then added under a steady stream of argon, followed by solvent (0.5 mL) and silane (0.75 mmol, 1.5 equiv). The vial was then sealed and the mixture was stirred at the indicated temperature for the indicated time. After the reaction was complete, the reaction mixture was diluted with diethyl ether (2 mL), filtered through a short pad of silica gel, and concentrated under reduced pressure. Volatiles were removed under high vacuum and the resultant material was purified by silica gel flash chromatography if necessary to give the desired O-Si product.The general procedure was followed. The reaction was performed with NaOH (4.0 mg, 0.1 mmol, 20 mol %), benzyl alcohol (54 mg, 0.5 mmol, 1.0 equiv), (t-Bu) Me2SiH (87 mg, 124 muL, 1.5 mmol, 3.0 equiv), 0.25 mL dimethylformamide (DMF) and 0.25 mL of tetrahydrofuran (THF) at 65 C. for 24 h. The desired product 2d (66.2 mg, 60% yield) was obtained as a colorless oil by silica gel flash chromatography (5% EtOAc in hexanes). Rf=0.42 (5% EtOAc in hexanes); 1H NMR (500 MHz, CDCl3) delta 7.35 (d, J=4.6 Hz, 4H), 7.28-7.24 (m, 1H), 4.78 (d, J=0.6 Hz, 2H), 0.98 (s, 9H), 0.14 (s, 6H). This compound has been previously characterized. See Yamamoto, K., et al., Bulletin of the Chemical Society of Japan, 1989, 62 (6), 2111-2113. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
>99% | With oxygen; In water; acetone; at 30℃; under 760.051 Torr; for 0.08333330000000001h; | General procedure: A typical reaction procedure for the oxidation of 1 to 2 using Au/HAP was as follows.Au/HAP (0.005 g, Au: 0.0415 mol%) was placed in a reaction vessel (50 cm3), followedby the addition of acetone (4 mL), water (0.1 mL), and 1 (1 mmol). The reactionmixture was vigorously stirred at 30 C under O2 atmosphere for 7 min. Au/HAP wasfiltered and the yield was determined by GC analysis. The product was isolated byKugelrohr distillation. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1H-imidazole; In N,N-dimethyl-formamide; at 25℃; for 24h; | [01658] A solution of 4,5-dimethyl-2-oxo-1,3-dioxolene (1 mmole) and selenium dioxide (2.5 mmole) in dioxane was heated at reflux for 1 h. Evaporation, extraction and chromatography gave 5-methyl-4-hydroxymethyl-2-oxo-1,3-dioxolene as a yellow oil. TLC: RPf=0.5, 5% MeOH-dichloromethane. [01659] A solution of 5-methyl-4-hydroxymethyl-2-oxo-1,3-dioxolene (1 mmole) in DMF was treated with tert-butyldimethylsilane (1.2 mmole) and imidazole (2.2 mmole) at 25 C. for 24 h. Extraction and chromatography gave 5-methyl-4-tert-butyldimethylsilyloxymethyl-2-oxo-1,3-dioxolene. [01660] A solution of 5-methyl-4-tert-butyldimethylsilyloxymethyl-2-oxo-1,3-dioxolene (1 mmole) and Lawesson's reagent (1.2 mmole) in toluene was heated to 120 C. for 12 h. Extraction and chromatography gave 5-methyl-4-tert-butyldimethylsilyloxymethyl-2-thio-1,3-dioxolene. [01661] A solution of 5-methyl-4-tert-butyldimethylsilyloxymethyl-2-thio-1,3-dioxolene in methanolic hydrogen chloride was stirred at 0 C. for 1 h and 25 C. for 12 h. Extraction and chromatography gave 5-methyl-4-hydroxymethyl-2-thio-1,3-dioxolene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine;palladium diacetate; In dichloromethane; at 20℃; | A suspension of t-butyldimethyl silane (0.3mL, 1. 85mmol), palladium (II) acetate (0. 013g, 0.06mmol) and triethyl amine (0.03mL, 0. 2mmol) in anhydrous dichloromethane (2mL) under argon was treated with a solution of 8-isopropyl-2,2, 4,4-tetramethyl-chroman-6-carboxylic acid 4- (2- benzyloxycarbonyl-vinyl)-phenyl ester (Intermediate 35,0. 063g, 0. 123mmol) in dichloromethane (2mL) and the resulting reaction mixture was stirred overnight at ambient temperature. The reaction mixture was quenched with water and extracted with diethyl ether. The organic extract was dried over anhydrous sodium sulfate, filtered and evaporated to a residue that was subjected to flash column chromatography to yield an intermediate that was treated with acetic acid (ImL) in water (0.3mL) and tetrahydrofuran (0.3mL) at ambient temperature for lh. The reaction mixture was diluted with water and extracted with ethyl acetate. The organic extract was dried over anhydrous sodium sulfate, filtered and evaporated to a residue that was subjected to preparative reverse phase HPLC using 10% water in acetonitrile as the mobile phase to afford the title compound (0.007g). 'H NMR (300 MHz, CDC13) : 5 7.89 (d, 1H, J= 2Hz), 7.74 (d, 1H, J= 2Hz), 7.67 (d, 1H, J= 15.8Hz), 7.49 (d, 2H, J= 8.8Hz), 7.15 (d, 2H, J= 8. 8Hz), 6.32 (d, 1H, J= 15. 8Hz), 3. 20 (heptet, 1H, J = 6.8Hz), 1.77 (s, 2H), 1.29 (s, 6H), 1.28 (s, 6H), 1.12 (d, 6H, J= 6. 8Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine;palladium diacetate; In dichloromethane; at 20℃; | 8-Isopropyl-2 2*4 4-tetramethyl-chroman-6-carboxYlic acid 4-(2-carboxv-vinyl .- phenyl ester (Compound 16); A suspension of t-butyldimethyl silane (0.3mL, 1.85mmol), palladium (II) acetate (0.013g, 0. 06mmol) and triethyl amine (0.03mL, 0. 2mmol) in anhydrous dichloromethane (2mL) under argon was treated with a solution of 8- isopropyl-2,2, 4, 4-tetramethyl-chroman-6-carboxylic acid 4- (2-benzyloxycarbonyl- vinyl) -phenyl ester (Intermediate 35,0. 063g, 0.123mmol) in dichloromethane (2mL) and the resulting reaction mixture was stirred overnight at ambient temperature. The reaction mixture was quenched with water and extracted with diethyl ether. The organic extract was dried over anhydrous sodium sulfate, filtered and evaporated to a residue that was subjected to flash column chromatography to yield an intermediate that was treated with acetic acid (1mL) in water (0.3mL) and tetrahydrofuran (0.3mL) at ambient temperature for lh. The reaction mixture was diluted with water and extracted with ethyl acetate. The organic extract was dried over anhydrous sodium sulfate, filtered and evaporated to a residue that was subjected to preparative reverse phase HPLC using 10% water in acetonitrile as the mobile phase to afford the title compound (0.007g). 1H NMR (300 MHz, CDC13) : 8 7.89 (d, 1H, J= 2Hz), 7.74 (d, 1H, J= 2Hz), 7.67 (d, 1H, J= 15.8Hz), 7.49 (d, 2H, J= 8. 8Hz), 7.15 (d, 2H, J = 8. 8Hz), 6.32 (d, 1H, J= 15.8Hz), 3.20 (heptet, 1H, J= 6.8Hz), 1.77 (s, 2H), 1.29 (s, 6H), 1.28 (s, 6H), 1.12 (d, 6H, J = 6. 8Hz) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.0% | With sodium carbonate; In 1-methyl-pyrrolidin-2-one; nitrogen; water; toluene; | Example 2 Synthesis of methyl (2S,3R)-2-aminomethyl-3-(t-butyl dimethylsilyloxy)butyrate, of the formula (V) where R1 is a t-butyl dimethylsilyl group and R2 is a methyl group. 5.51 g (30.0 mmoles) of methyl (2S,3R)-2-aminomethyl-3-hydroxybutyrate hydrochloride and 27.5 mg (0.5 wt. %) of 5% palladium silicoalumina were suspended in 30 of N-methyl pyrrolidone, heated to 80 C. and stirred in a nitrogen stream until the hydrochloride was dissolved. Subsequently, 3.84 g (33.0 mmoles) of <strong>[29681-57-0]t-butyldimethylsilane</strong> were added dropwise during a time period of 2 hours in a nitrogen stream. After the addition, the mixture was further stirred for 17 hours at 80 C. in a nitrogen stream, cooled to room temperature and concentrated in vacuo. The concentrate was supplemented with 50 ml of toluene and filtered with celite auxiliary filtering agent, to remove the catalyst. The filtrate was supplemented with 50 ml of 10% sodium carbonate solution and stirred for 30 minutes. After fractionating, the obtained toluene phase was washed with 30 ml of water and condensed in vacuo. The resulting crude product was distilled at 73 C. at a pressure of 40 Pa (0.3 mm Hg), to obtain 6.89 g (26.4 mmoles) of an oily product consisting of methyl (2S,3R)-2-aminomethyl-3-(t-butyldimethylsilyloxy)butyrate. Yield was 88.0%. The obtained product showed the following spectral features: IR (neat sample): 1740 cm-1 NMR (in CDCl3): 0.04 (S,3H); 0.06 (s, 3H); 0.87 (s, 9H); 1.18 (d, J=6.2 Hz, 3H); 2.45 (ddd, J=4.5 Hz, 6.7 Hz, 8.3 Hz, 1H); 2.98 (dd, J=4.5 Hz, 13.0 Hz, 1H); 3.04 (dd, J=8.3 Hz, 13.0 Hz, 1H); 3.70 (m, 1H); 4.12 (m, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With ammonium chloride; triethylamine; In dichloromethane; | EXAMPLE 10 STR31 To a dichloromethane solution (1.0 ml) of palladium (II) acetate (8.0 mg, 0.04 mmol) and triethylamine (15 mul, 0.11 mmol), <strong>[29681-57-0]t-butyldimethylsilane</strong> (179 mul, 1.1 mmol) was added and the mixture was stirred for 15 minutes at room temperature. To the resulting black suspension, a dichloromethane solution (1.0 ml) of N-allyloxycarbonylvaline methyl ester (154 mg, 0.72 mmol) was added and the mixture was stirred for an additional 15 hours. After a saturated aqueous solution of ammonium chloride was added to quench the reaction, extraction with ether was conducted and the ether layer was dried over anhydrous magnesium sulfate and filtered. By distilling off the solvent, N-t-butyldimethylsilyloxycarbonylvaline methyl ester was obtained in an amount of 207 mg (yield, 100%). The physical data for this compound were in agreement with those reported in Examples 4 and 9. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With ammonium chloride; triethylamine; In dichloromethane; | EXAMPLE 12 STR33 To a dichloromethane solution (1.0 ml) of palladium (II) acetate (8.0 mg, 0.04 mmol) and triethylamine (16 mul, 0.12 mmol), <strong>[29681-57-0]t-butyldimethylsilane</strong> (187 mul, 1.1 mmol) was added and the mixture was stirred for 15 minutes at room temperature in an argon atmosphere. To the resulting black suspension, a dichloromethane solution (1.0 ml) of N-allyloxycarbonylallylglycine methyl ester (150 mg, 0.75 mmol) was added and the mixture was stirred for an additional 20 hours. After a saturated aqueous solution of ammonium chloride was added to quench the reaction, extraction with ether was conducted and the ether layer was dried over anhydrous magnesium sulfate and filtered. By distilling off the solvent, N-t-butyldimethylsilyloxycarbonylallylglycine was obtained in an amount of 184 mg (yield, 90%). The physical data for this compound were in agreement with those reported in Examples 3 and 11. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With methanol; palladium diacetate; tricyclohexylphosphine In toluene at 80℃; for 10h; Inert atmosphere; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With palladium diacetate; triethylamine; In dichloromethane; at 60℃; for 4.0h;Inert atmosphere; | To the stirred solution of benzyl (1R,3aS ,5aR,5bR,7aR, 11 aS, 1 ibR, 1 3aR, 1 3bR)-9-(4- (methoxycarbonyl)phenyl)-5a,5b, 8,8,11 a-pentamethyl- 1 -(prop-i -en-2-yl)- 1,2,3,4,5 ,5a,5b,6,7, 7a,8, 11,11 a, 1 ib, 12,13,13 a, 1 3b-octadecahydro-3aH-cyclopenta[ajchrysene-3a-carboxylate(step 4, 6.0 g, 9.06 mmol, 1.0 eq) in DCM (90 mL) was added triethylamine (2 mL, 45.3 mmol, 1.6 eq) and tert. Butyldimethylsilane (3 mL, 18.12 mmol, 2.0 eq) at room temperature under nitrogen atmosphere. Then Pd(OAc)2 (1.0 g, 4.53 mmol, 0.5 eq) was added to the reaction mixture, heated to 60C and stirred for about 4 hours. TLC indicated starting material was consumed and the desired product was observed. The reaction mixture wasfiltered through a pad of celite and washed with CH2C12. The filtrate was evaporated under reduced pressure, the crude was dissolved in acetic acid (31.2 mL), THF (15 mL), water (6 mL) and stirred for about 1 hour at room temperature. Solid was separated which solid was filtered and washed with water to afford the desired product (6.0 g, 96.0%) as an off white solid. H? NMR (DMSO6, 300 MHz): oe 7.89 (d, 2H), 7.25 (d, 2H), 5.25 (d, 1H), 4.69 (s, 1H),4.58 (s, 1H), 3.84 (s, 3H), 2.12-2.03 (m, 3H), 1.78-1.62 (m, 5H), 1.49-1.23 (m, 19H), 0.97-0.88 (m, 25H), and 0.24 (s, 4H); Mass: [Mf? 687.10 (100%) |
91% | With triethylamine;palladium diacetate; In 1,2-dichloro-ethane; at 60℃; for 2.0h;Inert atmosphere; | To a solution of (lR,3aS,5aR,5bR,7aR,l laS,l lbR,13aR,13bR)-benzyl 9-(4- (methoxycarbonyl)phenyl)-5 a,5b,8, 8, 11 a-pentamethyl- 1 -(prop- 1 -en-2-yl)- 2,3,3a,4,5,5a,5b,6,7,7a,8,l l,l la,l lb,12,13,13a,13b-octadecahydro-lH- cyclopenta[a]chrysene-3a-carboxylate (3.82 g, 5.76 mmol) in dichloroethane (100 mL) was added triethylamine (1.285 mL, 9.22 mmol), <strong>[29681-57-0]ter<strong>[29681-57-0]t-butyldimethylsilane</strong></strong> (1.912 mL, 11.52 mmol), and palladium(II) acetate (0.647 g, 2.88 mmol). The mixture was flushed with N2, then was heated to 60 C. After 2h, the reaction was cooled to rt, was filtered through a pad of celite and silica gel to remove the solids which were washed with 25% EtOAc in hexanes. The filtrate was concentrated under reduced pressure and was treated with 20mL of acetic acid, 10 mL of THF and 3 mL of water. After stirring for lh the solids that formed were collected by filtration and were washed with water to give (lR,3aS,5aR,5bR,7aR, l laS, l IbR, 13aR, 13bR)-tert-butyldimethylsilyl 9-(4- (methoxycarbonyl)phenyl)-5a,5b,8,8, l la-pentamethyl-l-(prop-l-en-2-yl)- 2,3,3a,4,5,5a,5b,6,7,7a,8, l l, l la, l lb, 12, 13, 13a, 13b-octadecahydro-lH- cyclopenta[a]chrysene-3a-carboxylate (3.62 g, 5.27 mmol, 91 % yield) as a white solid. ¾ NMR (400 MHz, CHLOROFORM-d) delta ppm 0.28 - 0.32 (m, 6 H), 0.90 - 1.78 (m, 16 H), 0.94 (s, 6 H), 0.98 (s, 9 H), 0.99 (br. s., 3 H), 1.01 (s, 6 H), 1.71 (s, 3 H), 1.84 - 2.02 (m, 2 H), 2.06 - 2.17 (m, 1 H), 2.22 - 2.35 (m, 2 H), 3.08 (td, J=10.92, 4.27 Hz, 1 H), 3.92 (s, 4 H), 4.62 (s, 1 H), 4.75 (d, J=1.76 Hz, 1 H), 5.30 (dd, J=6.15, 1.63 Hz, 1 H), 7.21 (d, J=8.28 Hz, 2 H), 7.94 (d, J=8.28 Hz, 2 H). |
91% | With triethylamine;palladium diacetate; In 1,2-dichloro-ethane; at 60℃; for 2.0h;Inert atmosphere; | To a solution of (lR,3aS,5aR,5bR,7aR,llaS,llbR,13aR,13bR)-benzyl 9-(4- (methoxycarbonyl)phenyl)-5a,5b,8,8,l la-pentamethyl-l-(prop-l-en-2-yl)- 2,3,3a,4,5,5a,5b,6,7,7a,8,ll,lla,llb,12,13,13a,13b-octadecahydro-lH- cyclopenta[a]chrysene-3a-carboxylate (3.82 g, 5.76 mmol) in dichloroethane (100 mL) was added triethylamine (1.285 mL, 9.22 mmol), <strong>[29681-57-0]ter<strong>[29681-57-0]t-butyldimethylsilane</strong></strong> (1.912 mL, 11.52 mmol), and palladium(II) acetate (0.647 g, 2.88 mmol). The mixture was flushed with 2 and was heated to 60 C. After 2 h, the reaction was cooled to rt, was filtered through a pad of celite and silica gel to remove the solids which were washed with 25% EtOAc in hexanes. The filtrate was concentrated under reduced pressure and was treated with 20 mL of acetic acid, 10 mL of THF and 3 mL of water. After stirring for lh the solids that formed were collected by filtration and were washed with water to give (lR,3aS,5aR,5bR,7aR,l laS,l IbR, 13aR,13bR)-tert-butyldimethylsilyl 9-(4- (methoxycarbonyl)phenyl)-5a,5b,8,8,l la-pentamethyl-l-(prop-l-en-2-yl)- 2,3,3a,4,5,5a,5b,6,7,7a,8,ll,lla,llb,12,13,13a,13b-octadecahydro-lH- cyclopenta[a]chrysene-3a-carboxylate (3.62 g, 5.27 mmol, 91 % yield) as a white solid. ¾ NMR (400 MHz, CHLOROFORM-d) delta ppm 7.94 (d, J=8.28 Hz, 2 H), 7.21 (d, J=8.28 Hz, 2 H), 5.30 (dd, J=6.15, 1.63 Hz, 1 H), 4.75 (d, J=1.76 Hz, 1 H), 4.62 (s, 1 H), 3.92 (s, 4 H), 3.08 (td, J=10.92, 4.27 Hz, 1 H), 2.35 - 2.22 (m, 2 H), 2.17 - 2.06 (m, 1 H), 2.02 - 1.84 (m, 2 H), 1.71 (s, 3 H), 1.01 (s, 6 H), 0.99 (br. s., 3 H), 0.98 (s, 9 H), 0.94 (s, 6 H), 1.78 - 0.90 (m, 16 H), 0.32 - 0.28 (m, 6 H). |
91% | With triethylamine;palladium diacetate; In 1,2-dichloro-ethane; at 60℃; for 2.0h;Inert atmosphere; | Preparation of (lR,3aS,5aR,5bR,7aR,l laS,l lbR,13aR,13bR)-tert-butyldimethylsilyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,l 1 a-pentamethyl- l-(prop-l-en-2 -yl)- 2,3,3a,4,5,5a,5b,6,7,7a,8,l l,l la,l lb,12,13,13a,13b-octadecahydro-lH- cyclopenta[a]chrysene-3a-carboxylate. To a solution of (lR,3aS,5aR,5bR,7aR,llaS,llbR,13aR,13bR)-benzyl 9-(4- (methoxycarbonyl)phenyl)-5a,5b,8,8,l la-pentamethyl-l-(prop-l-en-2-yl)- 2,3,3a,4,5,5a,5b,6,7,7a,8,ll,lla,llb,12,13,13a,13b-octadecahydro-lH- cyclopenta[a]chrysene-3a-carboxylate (3.82 g, 5.76 mmol) in dichloroethane (100 mL) was added triethylamine (1.285 mL, 9.22 mmol), <strong>[29681-57-0]ter<strong>[29681-57-0]t-butyldimethylsilane</strong></strong> (1.912 mL, 11.52 mmol), and palladium(II) acetate (0.647 g, 2.88 mmol). The mixture was flushed with 2 and heated to 60 C. After 2 h, the reaction was cooled to rt, filtered through a pad of celite and silica gel to remove the solids which were washed with 25% EtOAc in hexanes. The filtrate was concentrated under reduced pressure and treated with acetic acid (25 mL), THF (10 mL) and water (3 mL). After stirring for 1 h the solids formed were collected by filtration and washed with water to give the title compound (3.62 g, 5.27 mmol, 91% yield) as a white solid. XH NMR (400 MHz, CHLOROFORM-d) delta ppm 7.94 (d, J=8.28 Hz, 2 H), 7.21 (d, J=8.28 Hz, 2 H), 5.30 (dd, J=6.15, 1.63 Hz, 1 H), 4.75 (d, J=1.76 Hz, 1 H), 4.62 (s, 1 H), 3.92 (s, 4 H), 3.08 (td, J=10.92, 4.27 Hz, 1 H), 2.35 - 2.22 (m, 2 H), 2.17 - 2.06 (m, 1 H), 2.02 - 1.84 (m, 2 H), 1.71 (s, 3 H), 1.01 (s, 6 H), 0.99 (br. s., 3 H), 0.98 (s, 9 H), 0.94 (s, 6 H), 1.78 - 0.90 (m, 16 H), 0.32 - 0.28 (m, 6 H). |
91% | With palladium diacetate; triethylamine; In 1,2-dichloro-ethane; at 60℃; for 2.0h;Inert atmosphere; | Step 5. Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-tert-butyldimethylsilyl 9-(4-(methoxycarbonyl)phenyl)-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]chrysene-3a-carboxylate [0353] (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-5 a,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]chrysene-3a-carboxylate (3.82 g, 5.76 mmol) in dichloroethane (100 mL) was added triethylamine (1.285 mL, 9.22 mmol), <strong>[29681-57-0]ter<strong>[29681-57-0]t-butyldimethylsilane</strong></strong> (1.912 mL, 11.52 mmol), and palladium(II) acetate (0.647 g, 2.88 mmol). The mixture was flushed with N2 and was heated to 60 C. After 2 h, the reaction was cooled to rt, was filtered through a pad of celite and silica gel to remove the solids which were washed with 25% EtOAc in hexanes. The filtrate was concentrated under reduced pressure and was treated with 20 mL of acetic acid, 10 mL of THF and 3 mL of water. After stirring for 1 h the solids that formed were collected by filtration and were washed with water to give (1R,3aS,5aR,5bR,7aR,11aS,11bR, 13aR,13bR)-tert-butyldimethylsilyl 9-(4-(methoxycarbonyl)phenyl)-5 a,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]chrysene-3a-carboxylate (3.62 g, 91% yield) as a white solid. 1H NMR (400 MHz, CHLOROFORM-d) delta ppm 7.94 (d, J=8.28 Hz, 2H), 7.21 (d, J=8.28 Hz, 2H), 5.30 (dd, J=6.15, 1.63 Hz, 1H), 4.75 (d, J=1.76 Hz, 1H), 4.62 (s, 1H), 3.92 (s, 4H), 3.08 (td, J=10.92, 4.27 Hz, 1H), 2.35-2.22 (m, 2H), 2.17-2.06 (m, 1H), 2.02-1.84 (m, 2H), 1.71 (s, 3H), 1.01 (s, 6H), 0.99 (br. s., 3H), 0.98 (s, 9H), 0.94 (s, 6H), 1.78-0.90 (m, 16H), 0.32-0.28 (m, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine;palladium diacetate; In dichloromethane; at 60℃; for 3.0h;Inert atmosphere; | A mixture of (lS,3aS,5aR,5bR,7aR,l laS,l lbR,13aR,13bR)-benzyl l-isopropyl-9- (4-(methoxycarbonyl)phenyl)-5a,5b,8,8, 11 a-pentamethyl- 2,3,3a,4,5,5a,5b,6,7,7a,8,l l,l la,l lb,12,13,13a,13b-octadecahydro-lH- cyclopenta[a]chrysene-3a-carboxylate (220 mg, 0.331 mmol), <strong>[29681-57-0]ter<strong>[29681-57-0]t-butyldimethylsilane</strong></strong> (77 mg, 0.662 mmol), TEA (0.074 mL, 0.529 mmol) and palladium (II) acetate (18.57 mg, 0.083 mmol) in DCM (2 mL) was heated up at 60 C for 3 h, TLC indicated the starting material was consumed. The reaction mixture was filtered a pad of celite. The filtrates were concentrated under reduced pressure to provide the intermediate. To this intermediate in dioxane (2 mL) was added TBAF (346 mg, 0.993 mmol), the reaction mixture was stirred for 2 h at room temperature. LCMS indicated the formation of desired product. The reaction mixture was quenched with distilled water (5 mL), extracted with DCM (3 x 8mL). All the extracts were combined, dried over sodium sulfate, filtered and concentrated under reduced pressure to provide the desired product as a pale yellow solid (150 mg, 79%). LCMS: m/e 575.35 (M+H)+, 2.84 min (method 1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,8-diazabicyclo[5.4.0]undec-7-ene; In dichloromethane; at 100℃; under 22801.5 Torr; for 4.0h;Autoclave; Inert atmosphere; | General procedure: Catalytic runs were performed in a 25 mL stainless steel autoclave fitted with a Teflon inner crucible and a stirring bar. In a typical run, 3 mmol of alcohol or amide, 3 mL of a freshly distilled CH2Cl2, 3 mmol of R3SiH, 0.3 mmol of DBU were put, via syringe and under CO atmosphere, in a Pyrex Schlenk tube. This solution was introduced in the autoclave, previously placed under vacuum (0.1 mmHg) and charged with 0.1 mol% of rhodium catalyst, by a steel siphon. The reactor was pressurised to 30 atm of CO and stirred at 100 C for the required times. The autoclave was then cooled to room temperature and the excess of CO was removed under fume hood. The reaction mixture was diluted with CH2Cl2, filtered on silica gel and concentrated under reduced pressure. The reagents conversion and the products composition were determined by GLC and 1H NMR. The purification of the crude oil by column chromatography on silica gel afforded the pure beta-lactones [38] and beta-lactams [50]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With 1H-imidazole; In N,N-dimethyl-formamide; at 20℃; | Into a 50-mL round-bottom flask was placed <strong>[128117-22-6]benzyl 3-hydroxyazetidine-1-carboxylate</strong> (2.15 g, 10.38 mmol, 1.00 equiv), TBSCl (2.34 g, 15.60 mmol, 1.50 equiv), imidazole (1.27 g, 18.68 mmol, 1.80 equiv) and N,N-dimethylformamide (15 mL). The resulting solution was stirred overnight at room temperature. The reaction was then quenched by the addition of 30 mL of water. The mixture was extracted with 3*40 mL of ethyl acetate and the organic layers combined. The resulting mixture was washed with 2*50 mL of sodium chloride (sat.). The mixture was dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was applied onto a silica gel column with ethyl acetate/petroleum ether (1:5). Purification afforded 3.0 g (90%) of benzyl 3-[(tert-butyldimethylsilyl)oxy]azetidine-1-carboxylate (50.3) as a light yellow liquid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With palladium diacetate; In water; ethyl acetate; | Step 2: Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-tert-butyldimethylsilyl 9-(4-(tert-butoxycarbonyl)phenyl)-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]chrysene-3a-carboxylate. Intermediate 5 To a solution of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-benzyl 9-(4-(tert-butoxycarbonyl)phenyl)-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]chrysene-3a-carboxylate (13.8 g, 19.57 mmol) in DCE (200 mL) was added triethylamine (4.37 mL, 31.3 mmol), <strong>[29681-57-0]ter<strong>[29681-57-0]t-butyldimethylsilane</strong></strong> (6.49 mL, 39.1 mmol), and palladium(II) acetate (1.099 g, 4.89 mmol). The mixture was flushed with nitrogen and was heated to 60 C. After 3.5 h of heating, the mixture was cooled to rt and was filtered through a pad of silica gel and celite which was washed with dichloromethane followed by 25% ethyl acetate in hexanes. The filtrate was concentrated under reduced pressure. The mixture was diluted with 200 mL of water and was extracted with dichloromethane (3*200 mL). The combined organic layers were dried with sodium sulfate, filtered, and concentrated under reduced pressure to give (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-tert-butyldimethylsilyl 9-(4-(tert-butoxycarbonyl)phenyl)-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]chrysene-3a-carboxylate (13.75 g, 18.86 mmol, 96% yield) as a white foam. 1H NMR (500 MHz, Chloroform-d) delta=7.87 (d, J=7.9 Hz, 2H), 7.16 (d, J=7.9 Hz, 2H), 5.26 (d, J=4.9 Hz, 1H), 4.73 (d, J=1.5Hz, 1H), 4.60 (s, 1H), 3.06 (td, J=10.9, 4.7 Hz, 1H), 2.31-2.22 (m, 2H), 2.09 (dd, J=17.2, 6.3 Hz, 1H), 1.98-1.82 (m, 2H), 1.69 (s, 3H), 1.58 (s, 9H), 0.99 (s, 6H), 0.96 (br. s., 3H), 0.96 (s, 9H), 0.91 (s, 6H), 1.76-0.88 (m, 17H), 0.28 (s, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With hydrogenchloride; tetrabutyl ammonium fluoride; palladium diacetate; In 1,4-dioxane; water; | Step 2. Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(3-fluoro-4-(methoxycarbonyl)phenyl)-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]chrysene-3a-carboxylic acid To a solution of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-benzyl 9-(3-fluoro-4-(methoxycarbonyl)phenyl)-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]chrysene-3a-carboxylate (3.59 g, 5.27 mmol) in DCE (25 mL) was added TEA (1.176 mL, 8.44 mmol), <strong>[29681-57-0]t-butyldimethylsilane</strong> (1.749 mL, 10.54 mmol), and palladium(II) acetate (0.118 g, 0.527 mmol). The mixture was flushed with N2 and heated to 60 C. for 1 h. The mixture was cooled to rt and was filtered through a plug of celite and silica gel (washed with 25% EtOAc in hexanes). The filtrate was concentrated under reduced pressure. The residue was diluted with 25 mL of dioxane and TBAF (75% in water) (2.76 g, 7.91 mmol) was added. The mixture was stirred for 30 minutes at rt then was diluted with 50 mL of 1N HCl. The solids that formed were collected by filtration and were washed with water to give the title compound (2.95 g, 4.99 mmol, 95% yield) as a white solid. 1H NMR (400 MHz, CHLOROFORM-d) delta ppm 7.83 (1H, t, J=7.9 Hz), 6.90-7.00 (2H, m), 5.34 (1H, dd, J=6.1, 1.6 Hz), 4.77 (1H, d, J=2.0 Hz), 4.64 (1H, s), 3.94 (3H, s), 3.04 (1H, td, J=10.7, 4.8 Hz), 2.24-2.34 (2H, m), 2.13 (1H, dd, J=17.3, 6.3 Hz), 1.96-2.06 (2H, m), 1.72 (3H, s), 1.03 (3H, s), 1.02 (3H, s), 0.98 (3H, s), 0.93-0.96 (6H, m), 0.91-1.80 (17H, m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With triethylamine; In 1,2-dichloro-ethane; | Step 3. Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-tert-butyldimethylsilyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(1-methylcyclopropyl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate. To a solution of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(1-methylcyclopropyl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (5.34 g, 7.89 mmol) in 1,2-dichloroethane (100 mL) were added triethylamine (1.76 mL, 12.6 mmol), <strong>[29681-57-0]ter<strong>[29681-57-0]t-butyldimethylsilane</strong></strong> (2.62 mL, 1.84 g, 15.8 mmol) and palladium (II) acetate (0.443 g, 1.97 mmol). The mixture was heated to 60 C. for 22 h. The crude reaction mixture was passed through a silica gel/celite plug with 10:1 hexanes:EtOAc as the eluent. Concentration in vacuo gave 6.34 g (>100% yield) of a white solid which was carried to the next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With palladium diacetate; acetic acid; In tetrahydrofuran; water; | Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-tert-butyldimethylsilyl 9-(4-(methoxycarbonyl)phenyl)-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]chrysene-3a-carboxylate. Intermediate 2 To a solution of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-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]chrysene-3a-carboxylate (3.82 g, 5.76 mmol) in dichloroethane (100 mL) was added triethylamine (1.285 mL, 9.22 mmol), <strong>[29681-57-0]ter<strong>[29681-57-0]t-butyldimethylsilane</strong></strong> (1.912 mL, 11.52 mmol), and palladium(II) acetate (0.647 g, 2.88 mmol). The mixture was flushed with N2 and heated to 60 C. After 2 h, the reaction was cooled to rt, filtered through a pad of celite and silica gel to remove the solids which were washed with 25% EtOAc in hexanes. The filtrate was concentrated under reduced pressure and treated with acetic acid (25 mL), THF (10 mL) and water (3 mL). After stirring for 1 h the solids formed were collected by filtration and washed with water to give the title compound (3.62 g, 5.27 mmol, 91% yield) as a white solid. 1H NMR (400 MHz, CHLOROFORM-d) delta ppm 7.94 (d, J=8.28 Hz, 2H), 7.21 (d, J=8.28 Hz, 2H), 5.30 (dd, J=6.15, 1.63 Hz, 1H), 4.75 (d, J=1.76 Hz, 1H), 4.62 (s, 1H), 3.92 (s, 4H), 3.08 (td, J=10.92, 4.27 Hz, 1H), 2.35-2.22 (m, 2H), 2.17-2.06 (m, 1H), 2.02-1.84 (m, 2H), 1.71 (s, 3H), 1.01 (s, 6H), 0.99 (br. s., 3H), 0.98 (s, 9H), 0.94 (s, 6H), 1.78-0.90 (m, 16H), 0.32-0.28 (m, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With lithium diisopropyl amide; In tetrahydrofuran; at -78 - 20℃;Inert atmosphere; | General procedure: A 250 mL two-neck round bottom flask equipped with a magnetic stirrer bar, a septum and nitrogen tee connected to an argon source was charged with 2,2,2-trifluoroethyl p-toluenesulfonate (3.00 g, 11.8 mmol) and 120mL of THF. After the reaction mixture was cooled down to -78 C, LDA (2.0 M solution, 13.0 mL, 26.0 mmol) was added dropwise and then stirred at -78 C for 30 min. Trialkylsilane (11.9 mmol) was added dropwise at -78 C, followed by slowly warming to room temperature. The mixture was quenched with 50 mL of NH4Cl water solution, extracted with 100 mL of ether twice, dried over anhydrous MgSO4 and chromatographed on SiO2 column. Elution with n-hexane and ethyl acetate (10:1) provided 2,2-difluoro-1-trialkylsilylethenyl p-toluenesulfonates 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
27%Spectr. | With 1,4-bis-(trimethylsilyl)benzene; chloro[N-[4-(dimethylamino)phenyl]-2-pyridinecarboxamidato](pentamethylcyclopentadienyl)iridium; hydrogen; lithium trifluoromethanesulfonate; N-ethyl-N,N-diisopropylamine; In benzene-d6; at 60℃; under 3040.2 Torr; for 48.0h; | General procedure: J. Young In a NMR sample tube with a bulb,Chloro [N- [4- (dimethylamino) phenyl] -2-pyridinecarboxamidato] (pentamethylcyclopentadienyl) iridium (3.6 mg, 0.006 mmol), Lithium trifluoromethanesulfonate (0.9 mg, 0.006 mmol), and 1,4-bis (trimethylsilyl) benzene (6.7 mg, 0.03 mmol) in dibenzene (0.5 mL) was prepared and diisopropylethylamine (8.5 mg, 11.5 muL, 0.066 mmol) and 0.060 mmol of silane shown in the following Table 1 were added. After freezing and deaerating the NMR tube, hydrogen (4 atm) was introduced, and the reaction was carried out at a temperature of 60 C. for 48 hours. 1 H, 29 Si NMR measurement to the corresponding hydrosilane compound was formed. The respective yields are shown in Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With palladium diacetate; triethylamine; In dichloromethane; at 60℃; for 4.0h;Inert atmosphere; | The stirred solution of benzyl (1R,3aS ,5aR,5bR,7aR, 11 aS, 1 lbR, 1 3aR, 1 3bR)-9-(4- (methoxycarbonyl)phenyl)-5a,5b, 8,8,11 a-pentamethyl- 1 -(1 -methylcyclopropyl)- 1,2,3,4,5 ,5a, 5b,6,7,7a,8, 11,11 a, 1 ib, 12,13,1 3a, 1 3b-octadecahydro-3aH-cyclopenta[ajchrysene-3 acarboxylate (step 4, 1.0 g, 1.47 mmol, 1.0 eq) in DCM (15 mL) was added triethylamine(0.32 mL, 2.35 mmol, 1.6 eq) and tert. butyl dimethylsilane (0.47 mL, 2.95 mmol, 2.0 eq) at room temperature under nitrogen atmosphere then Pd (OAc)2 (0.16 g, 7.35 mmol, 0.5 eq) was added to the reaction mixture, heated to 60C and stirred for about 4 hours. TLC indicated starting material was consumed and the desired product was observed. The reaction mixture was filtered through a pad of celite and washed with CH2C12. The filtrate wasevaporated under reduced pressure and the crude was dissolved in acetic acid (5.2 mL), THF (2.6 mL) and water (1.3 mL) and stirred for about 1 hour at room temperature. The solid was separated, filtered and washed with water to afford the desired product (1.0 g, 98.0%) as a white solid. H? NMR (CDC13, 300 MHz): oe 7.94 (d, 2H), 7.21 (d, 2H), 5.31 (d, 1H), 3.91 (s, 3H), 2.25-2.09 (m, 3H), 2.23-2.10 (m, 2H), 2.00 (bs, 1H), 1.83-1.76 (m, 1H), 1.68-1.63 (m,2H), 1.56 (ds, 4H), 1.51-1.43 (m, 4), 1.36-1.25 (m, 8H), 1.01-0.85 (m, 28H), 0.40-0.31 (m,2H), 0.26 (s, 6H) and 0.06 (s, 2H); Mass: [M+Hj 700.10 (100%). |
98% | With palladium diacetate; triethylamine; In dichloromethane; at 60℃; for 4.0h;Inert atmosphere; | Step 5: Synthesis of tert-butyldimethylsilyl (lR,3aS,5aR,5bR, 7aR,llaS,llbR,13aR,13bR)-9- (4-(methoxycarbonyl)phenyl)-5a,5b,8,8,lla-pentamethyl-l-(l-methylcyclopropyl)-l,2,3,4,5, 5a,5b,6,7, 7a,8, 11,11 a,l lb, 12, 13,13a,13b-octadecahydro-3aH-cyclopenta[a]chrysene-3a- carboxylate: To the stirred solution of benzyl (lR,3aS,5aR,5bR,7aR,l laS,l lbR,13aR,13bR)-9-(4- (methoxycarbonyl)phenyl)-5a,5b, 8, 8, l la-pentamethyl-l-(l-methylcyclopropyl)- 1,2,3,4,5, 5a, 5b,6,7,7a,8,l 1,1 la,l lb, 12,13, 13a,13b-octadecahydro-3aH-cyclopenta[a]chrysene-3a- carboxylate (step 4, 1.0 g, 1.47 mmol, 1.0 eq) in DCM (15 mL) was added Triethylamine (0.32 mL, 2.35 mmol, 1.6 eq) and tert. Butyl dimethylsilane (0.47 mL, 2.95 mmol, 2.0 eq) at room temperature under nitrogen atmosphere, then Pd(OAc)2 (0.16 g, 7.35 mmol, 0.5 eq) was added to reaction mixture. Then the reaction was heated to 60 C and stirred for about 4 hours. TLC indicated starting material was consumed and the desired product was observed. The reaction mixture was filtered through a pad of celite and washed with CH2C12. The filtrate was evaporated under reduced pressure, the crude was dissolved in acetic acid (5.2 mL), THF (2.6 mL), water (1.3 mL) and stirred for about 1 hour at room temperature. Solid was separated, filtered and washed with water to give the desired product (1.0 g, yield: 98.0%) as an off white solid. H1 NMR (CDC13, 300 MHz): delta 7.94 (d, 2H), 7.21 (d, 2H), 5.31 (d, 1H), 3.91 (s, 3H), 2.25-2.09 (m, 3H), 2.23-2.10 (m, 2H), 2.00 (bs, 1H), 1.83-1.76 (m, 1H), 1.68-1.63 (m, 2H), 1.56 (ds, 4H), 1.51-1.43 (m, 4), 1.36-1.25 (m, 8H), 1.01-0.85 (m, 28H), 0.40-0.31 (m, 2H), 0.26 (s, 6H) and 0.06 (s, 2H); Mass: [M+H]+ 700.10 (100%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With 1H-imidazole; In dichloromethane; at 20℃; for 0.166667h;Cooling with ice; | 3-Bromopropanol (4.14 g, 30 mmol),Was added to DCM (50 mL), imidazole (2.5 g, 30 mmol) was added, stirred under ice for 10 min, TBDMS (4.5 g, 30 mmol) was added and the reaction was continued at room temperature. The next day, DCM (50 mL) (30 mL X3), dried over anhydrous magnesium sulfate and concentrated to give 7 g of a colorless oil in 92% yield |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With copper(I) oxide; di-tert-butyl peroxide In <i>tert</i>-butyl alcohol at 120℃; for 24h; Sealed tube; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1H-imidazole In N,N-dimethyl-formamide at 20℃; Cooling with ice; | 1.8 (8) Compound 11 (2 g, 11.9 mmol) and imidazole (2.02 g, 29.7 mmol) were dissolved in 10 mL anhydrous DMF.tert-Butyldimethylsilane (4.5 g, 29.7 mmol) was dissolved in 5 ml of anhydrous DMF.The ice bath is slowly added.The reaction solution was allowed to stir at room temperature overnight.After confirming the completion of the reaction through the TLC plate,After the reaction solution is suspended, the product is separated and purified by column chromatography to obtain a compound 12; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With lithium hexamethyldisilazane; In tetrahydrofuran; at 20℃; for 72.0h;Cooling with ice; Inert atmosphere; | 1 -(4-chloro-3-(trifluoromethyl)phenyl)propan-1 -one (10.1 g, 42.6 mmol, Intermediate 2) was dissolved in 80 mL of THF and cooled in a dry ice bath before addition of 42.6 mL (42.6 mmol) of 1 N lithium hexamethyldisilazane (in THF). After 1 h, a solution of 6.42 g of fer<strong>[29681-57-0]t-butyldimethylsilane</strong> (42.6 mmol) in 10 mL THF was added dropwise and the reaction was stirred, warming to room temperature. After 3 d, the reaction mixture was concentrated and hexane was added and the mixture was stirred 30 min before filtering and concentrating. Chromatography with hexane on silica gel pretreated with Et3N yielded 1 1.2 g of product (75%). 1 H NMR (400 MHz, CDCI3) delta 7.80 (d, J = 2.0 Hz, 1H), 7.55 (dd, J = 8.4, 2.0 Hz, 1H), 7.43 (d, J = 8.4 Hz, 1H), 5.33 (q, J = 6.9 Hz, 1H), 1.77 (d, J = 6.9 Hz, 3H), 1.02 (s, 9H), 0.00 (s, 6H). 19F NMR (376 MHz, CDCI3) delta -62.68. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | A solution of 4-fluoro-3-trifluoromethylpropiophenone (12 g, 55 mmol, CAS 239107-27-8) was dissolved in 60 mL of THF and cooled in a dry ice bath before addition of 60 mL (60 mmol) of 1 N lithium hexamethyldisilazane (in THF). After 1 h, a solution of 9.0 g of tert- butyldimethylsilane (60 mmol) in 15 mL THF was added dropwise and the reaction was stirred, warming to room temperature overnight. The next day, the reaction mixture was concentrated and stirred in 500 mL of hexane for 30 min before filtering and concentrating. Chromatography with hexane on silica gel pretreated with Et3N yielded 15.3 g product (84%). 1 H NMR (400 MHz, CDCI3) delta 7.71 (dd, J = 6.9, 2.1Hz, 1H), 7.62 (ddd, J = 7.3, 4.7, 2.2 Hz, 1H), 7.13 (t, J = 9.4 Hz, 1H), 5.26 (q, J = 6.9 Hz, 1H), 1.76 (d, J = 6.9 Hz, 3H), 1.02 (s, 9H), -0.00 (s, 6H). 19F NMR (376 MHz, CDCI3) delta -61.49 (d, J = 12.7 Hz), -1 16.85 (q, J = 12.8 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With silver trifluoromethanesulfonate; In dichloromethane; at 60℃; for 1.0h; | AgOTf (0.0125 mmol, 0.0013 g) was added to the reaction flask, dichloromethane (DCM, 2.5 ml) was added, and then 2.5 mmol of compound 1j (0.2907 g) was slowly added dropwise to the reaction flask and stirred at 60 C. After reacting for 1 hour, the product 2j (0.2598 g) was obtained by distillation under reduced pressure after the reaction was completed, and the yield was 90%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With dimanganese decacarbonyl; In neat (no solvent); at 160℃; for 12.0h;Sealed tube; Inert atmosphere; | General procedure: To an oven-dried sealed tube, 1 (3 mmol), 2 (1 mmol), Mn2(CO)10 (5 mol%, 0.05 mmol) were added under Ar and the mixture was then stirred at 160 oC for 12 h. After the reaction finished (as monitored by TLC), the product was purified by column chromatography on silica gel to afford the product 3. (Eluent: hexane). |
Tags: 29681-57-0 synthesis path| 29681-57-0 SDS| 29681-57-0 COA| 29681-57-0 purity| 29681-57-0 application| 29681-57-0 NMR| 29681-57-0 COA| 29681-57-0 structure
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