samarium

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a nitrogen environment, about 330 mg (2.20 mmole) of samarium and about 500 mg (1.77 mmole) of 1,2-diiodoethane is disposed in a round-bottomed flask. About 20 ml of tetrahydrofuran is added into the round-bottomed flask. The mixture in the round-bottomed flask is stirred until a deep-blue samarium diiodide solution is obtained. Following the process flow described in Example 1, about 348 mg (1.20 mmole) of benzoylferrocene reacts with about 242 mg (2.0 mmole) of allyl bromide to produce oil-type 1-Ferrocenyl-1-phenyl-1,3-butadiene (3c) with a weight of about 373 mg (1.19 mmole) and a yield of about 99%. is obtained

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: By reacting 0.85 mmole of phenyl benzoate in 6 ml of DME with 3.38 m atoms of samarium, in the conditions of example 9, a dark-brown compound (phenyl benzoate-samarium) has been obtained and treated as usually. Benzoate was quantitatively converted.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Example 1 is repeated, but with the use of 20 m.g atoms of samarium powder instead of ytterbium. Anthracene samarium (1/1) solvated with DME, is obtained as a purple compound with a substantially quantitative yield with respect to anthracene. The complex, treated with a water excess, gives dihydroanthracene with a quantitative yield.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred suspension of samarium metal (758 mg, 5.0 mmol) and 3 Å molecular sieves (0.5 g) in anhydrous tetrahydrofuran (THF, 9.5 mL) was slowly added a solution of 1,2-diiodoethane (1.3 g, 4.6 mmol) in THF (9.5 mL) at ambient temperature. After the reaction stirred for 30 min, hexamethylphosphoramide (HPMA, 3.0 mL, 17.2 mmol) was added to the reaction mixture and continued stirring for an additional 20 min. Then, a solution of ketone 1 (500.0 mg, 1.16 mmol) in THF (6.0 mL) was added followed by a solution of 1-bromo-5-methylhexane (208.0 mg, 1.16 mmol) in THF (2.0 mL). The reaction was allowed to stir for an additional hour until the starting material was completely consumed. After this, the reaction mixture was slowly treated with saturated NaHCO3, filtered through Celite and rinsed three times with an excess amount of diethyl ether. The filtrate was treated with water and extracted with diethyl ether. The ether extracts were washed with brine, dried over Na2SO4 and evaporated in vacuo to give a residue which was purified via silica gel chromatography. Elution with hexane-diethyl ether (4:1, v/v) afforded compound 2 (350.0 mg, 0.6 mmol, 57%) as a white powder (Honda et al. (1996) J. Chem. Soc., Perkin Trans. 1, 2291-2296). continued stirring for an additional 20 min to stir for an additional hour until the starting material was completely consumed After this, the reaction mixture was slowly treated with saturated NaHCO3 filtered through Celite rinsed three times with an excess amount of diethyl ether The filtrate was treated with water extracted with diethyl ether The ether extracts were washed with brine dried over Na2SO4 evaporated in vacuo to give a residue which was purified via silica gel chromatography Elution with hexane-diethyl ether (4:1

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 1,2-diiodoethane (42 mg, 0.15 mmol) in dry THF (1 mL) was added dropwise to a stirred mixture of samarium metal (46.5 mg, 0.31 mmol) in dry THF (1 mL) and stirred for 1.5 hours. The reaction mixture was then cooled to -78° C. (dry ice/acetone) and treated with a solution of 17-ethyl-1,14-dihydroxy-12-[2'-(4"-(naphth-2-yl)-3"-methoxycyclohexyl)-1 '-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9 ]octacos-18-ene-2,3,10,16-tetraone (100 mg, 0.109 mmol) in 1:1 THF/CH3OH. The mixture was maintained at -78° C. for 15 minutes then allowed to warm to room temperature. The reaction was quenched with cold saturated aqueous K2CO3 and quickly extracted with CH2Cl2. The extracts were combined, dried with Na2SO4, filtered and concentrated in vacuo. Purified by preparative TLC on silica gel (eluted with 7% CH3OH in CH2Cl2) to give 22 mg of 17-ethyl-1,2,14-trihydroxy-12-[2'-(4"-(naphth-2-yl)-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9 ]octacos-18-ene-3,10,16-trione (1H NMR and mass spectral analysis are consistent with the desired structure). to warm to room temperature The reaction was quenched with cold saturated aqueous K2CO3 quickly extracted with CH2Cl2 dried with Na2SO4 filtered concentrated in vacuo Purified by preparative TLC on silica gel (eluted with 7% CH3OH in CH2Cl2)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 1,2-diiodoethane (42 mg, 0.15 mmol) in dry THF (1 mL) was added dropwise to a stirred mixture of samarium metal (46.5 mg, 0.31 mmol) in dry THF (1 mL) and stirred for 1.5 hours. The reaction mixture was then cooled to -78° C. (dry ice/acetone) and treated with a solution of 17-ethyl-1,14-dihydroxy-12-[2'-(4"-(naphth-2-yl)-3"-methoxycyclohexyl)-1 '-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9 ]octacos-18-ene-2,3,10,16-tetraone (100 mg, 0.109 mmol) in 1:1 THF/CH3OH. The mixture was maintained at -78° C. for 15 minutes then allowed to warm to room temperature. The reaction was quenched with cold saturated aqueous K2CO3 and quickly extracted with CH2Cl2. The extracts were combined, dried with Na2SO4, filtered and concentrated in vacuo. Purified by preparative TLC on silica gel (eluted with 7% CH3OH in CH2Cl2) to give 22 mg of 17-ethyl-1,2,14-trihydroxy-12-[2'-(4"-(naphth-2-yl)-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9 ]octacos-18-ene-3,10,16-trione (1H NMR and mass spectral analysis are consistent with the desired structure). to warm to room temperature The reaction was quenched with cold saturated aqueous K2CO3 quickly extracted with CH2Cl2 dried with Na2SO4 filtered concentrated in vacuo Purified by preparative TLC on silica gel (eluted with 7% CH3OH in CH2Cl2)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 960 mg (4.8 mmol) of 5-acetyl-2-bromopyridine, 676 mg (5.28 mmol) of thiophene 3-boronic acid, 222 mg (0.19 mmol) of tetrakis(triphenylphosphine) palladium and 995 mg (7.2 mmol) of potasium carbonate in 13 ml of dioxane and 3 ml of water, was heated at 90° C. overnight. Brine was added and extracted three times with ethyl acetate. The organic phase was dried over Na2SO4, filtered and concentrated in vacuo. To a solution of the crude and 475 mg (14.4 mmol) of lithium cyanide in 16 ml of THF, 2.2 ml (14.4 mmol) of diethylcyanophosphonate was added neat at ambient temperature. The mixture was stirred at ambient temperature for 30 min. Water was added and extracted with a 1:1 solution of ethyl acetate/hexane. The organic solution was dried over Na2SO4 filtered and concentrated in vacuo. The crude was disolved in 10 ml of THF and added dropwise to a solution of samarium iodide, prepared from 3.32 g (22.08 mmol) of samarium and 3.89 g (13.8 mmol) of 1,2-diiodoethane. The mixture was stirred for 1 h. A 2.5 N solution of hydrochloric acid was added and extracted three times with diethyl ether. The organic phase was washed with a 1 N solution of sodium thiosulfate. The organic solution was dried over Na2SO4 filtered and concentrated in vacuo. Chromatography (100 g of silica gel, 25% ethyl acetate/hexane) of the residue afforded 225 mg (22%) of the title compound. B. To an ambient temperature solution of 214 mg (1 mmol) of material prepared in step A in 5 ml of THF was added dropwise 0.11 ml of a 10 M solution borane-methyl sulfide complex (1.1 mmol) in THF. The mixture was stirred at ambient temperature for 2 h. Then, 0.1 ml of a 10 M solution borane-methyl sulfide complex (1.0 mmol) in THF were added and the mixture stirred overnight. A saturated solution of hydrochloric acid in methanol (5 ml) was added, and stirred for 10 min. The solution was concentrated in vacuo. The crude was disolved in dichloromethane (5 ml) and cooled to 0° C., triethylamine 0.44 ml (3.2 mmol) was added, followed by isopropylsulfonyl chloride (0.14 ml, 1.2 mmol). The ice-bath was removed and the solution was stirred at ambient temperature for 2 h. The organic solution was washed with 1N hydrochloric acid, sodium bicarbonate saturated solution, brine, dried over Na2SO4 filtered and concentrated in vacuo. Chromatography (50 g of silica gel, 33% ethyl acetate/hexane) of the residue afforded 25 mg (7%) of the title compound. Field Desorption Mass Spectrum: M=324. extracted three times with ethyl acetate The organic phase was dried over Na2SO4 filtered concentrated in vacuo extracted with a 1:1 solution of ethyl acetate/hexane The organic solution was dried over Na2SO4 filtered concentrated in vacuo added dropwise to a solution of samarium iodide The mixture was stirred for 1 h extracted three times with diethyl ether The organic phase was washed with a 1 N solution of sodium thiosulfate The organic solution was dried over Na2SO4 filtered concentrated in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In the preparative method, 10 liters of a solution containing 19.8 g/l samarium in dilute nitric acid are charged to the vessel. The solution pH is adjusted to about 3 with ammonium bicarbonate, heat is applied to obtain a solution temperature of about 60° C., and about 200 grams of samarium carbonate are added. The impeller is started and a 2M solution of ammonium bicarbonate is pumped through the distributor, at a rate of about 49 ml/minute, until a pH of about 6 is obtained. The addition of ammonium bicarbonate is stopped and, under continued vessel agitation, the vessel is drained to leave a total slurry volume of about 5 liters. Agitation is stopped, the crystals are allowed to settle, and clear solution is decanted to leave a proper amount of crystals for the next batch preparation. After adjusting the pH of slurry in the vessel to a value less than about 5, samarium solution for the next batch is added. All batches after the first are precipitated at a temperature of 40° C. are charged to the vessel heat

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In the preparative method, 10 liters of a solution containing 19.8 g/l samarium in dilute nitric acid are charged to the vessel. The solution pH is adjusted to about 3 with ammonium bicarbonate, heat is applied to obtain a solution temperature of about 60° C., and about 200 grams of samarium carbonate are added. The impeller is started and a 2M solution of ammonium bicarbonate is pumped through the distributor, at a rate of about 49 ml/minute, until a pH of about 6 is obtained. The addition of ammonium bicarbonate is stopped and, under continued vessel agitation, the vessel is drained to leave a total slurry volume of about 5 liters. Agitation is stopped, the crystals are allowed to settle, and clear solution is decanted to leave a proper amount of crystals for the next batch preparation. After adjusting the pH of slurry in the vessel to a value less than about 5, samarium solution for the next batch is added. All batches after the first are precipitated at a temperature of 40° C. are charged to the vessel heat

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a nitrogen environment, about 330 mg (2.20 mmole) of samarium and about 500 mg (1.77 mmole) of 1,2-diiodoethane is disposed in a round-bottomed flask. About 20 ml of tetrahydrofuran is added into the round-bottomed flask. The mixture in the round-bottomed flask is stirred until a deep-blue samarium diiodide solution is obtained. Following the process flow described in Example 1, about 348 mg (1.20 mmole) of benzoylferrocene reacts with about 242 mg (2.0 mmole) of allyl bromide to produce oil-type 1-Ferrocenyl-1-phenyl-1,3-butadiene (3c) with a weight of about 373 mg (1.19 mmole) and a yield of about 99%. is obtained