1-tert-butyl-2-methoxybenzene

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

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: To a suspension of 2-t-butylphenol (20.00 g, 0.133 mol) and K2CO3 (36.80 g, 0.266 mol) in 260 mL of anhydrous acetone was added a neat solution of dimethylsulfate (17.63 g, 0.140 mol) dropwise through a syringe over 5 minute at RT under argon. The resulting thick suspension was stirred over night at RT and 100 mL of EtOH was added. After 1 hour, the mixture was diluted with ether and water. The aqueous layer was extracted with EtOAc. The combined organic layers were washed with water, brine and dried with MgSO4. After filtration, the solvents were removed and dried under high vacuum to give afford 2-t-butylanisole (16.99 g, 78% yield). 1H NMR (300 MHz, CDCl3): δ 1.40 (s, 9H), 3.86 (s, 3H), 6.88–6.96 (m, 2H), 7.18–7.26 (m, 1H), 7.31 (dd, J1=7.5 Hz, J2=1.2 Hz, 1H). The aqueous layer was extracted with EtOAc The combined organic layers were washed with water, brine dried with MgSO4 After filtration the solvents were removed dried under high vacuum to give

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

Procedure: To a solution of 2-(t-butyl)anisole (16.38 g, 0.0997 mol) in CH2Cl2 (350 mL) was added pyridinium tribromide (35.09 g, 0.110 mol). The resulting mixture was allowed to stir at RT overnight. The mixture was diluted with CH2Cl2 and H2O and the layers were separated, the aqueous layer was extracted with CH2Cl2 (2×). The combined organic layers were washed with H2O, brine and dried with MgSO4. The mixture was filtered and the solvents evaporated to give 2-(t-butyl)-4-bromoanisole as an oil (23.16 g, 95%). 1H NMR (300 MHz, CDCl3): δ 1.35 (s, 9H), 3.82 (s, 3H), 6.74 (d, J=8.7 Hz, 1H), 7.28 (dd, J1=8.7 Hz, J2=2.4 Hz, 1H), 7.35 (d, J=2.4 Hz, 1H). the layers were separated the aqueous layer was extracted with CH2Cl2 (2×) The combined organic layers were washed with H2O, brine dried with MgSO4 The mixture was filtered the solvents evaporated

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

Procedure: To Eaton's reagent obtained from 118 g of P4O10 and 600 ml of methanesulfonic acid a mixture of 70.3 g (0.428 mol) of 1-tert-butyl-2-methoxybenzene and 295.0 g (3.43 mol, 8 eqv.) of methacrylic acid was added for ca. 1 h at 50-55° C. The resulting mixture was stirred for 0.5 h at this temperature, then cooled to room temperature, and poured on a mixture of 1.5 liter of cold water and 2 kg of ice. After the ice melts, the precipitated crude 6-tert-butyl-5-methoxy-2-methylindan-1-one was filtered off and then washed with 2×100 ml of cold water. The crude product was dissolved in 500 ml of dichloromethane, and this solution was washed by aqueous K2CO3, dried over anhydrous K2CO3, and then evaporated on Rotavap. The residue was distilled in vacuum to give 70.6 g of crude 6-tert-butyl-5-methoxy-2-methylindan-1-one, b.p. 155-165° C./5 mm Hg. This product was dissolved in 200 ml of hot hexanes. Crystals precipitated from this solution at 5° C. were collected, washed by 50 ml of cold hexanes, and dried in vacuum. This procedure gave 64.1 g (65%) of the analytically pure substituted indanone. was added for ca. 1 h at 50-55° C the precipitated crude 6-tert-butyl-5-methoxy-2-methylindan-1-one was filtered off washed with 2×100 ml of cold water The crude product was dissolved in 500 ml of dichloromethane this solution was washed by aqueous K2CO3 dried over anhydrous K2CO3 evaporated on Rotavap The residue was distilled in vacuum

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

Procedure: To an Eaton's reagent obtained from 110 g of P4O10 and 560 ml of methanesulfonic acid a mixture of 65.6 g (0.399 mol) of 1-tert-butyl-2-methoxybenzene and 43.0 g (0.50 mol) of methacrylic acid was added for ca. 1 h at 50-55° C. The resulting mixture was stirred for 1 h at this temperature, then cooled to room temperature, and poured on a mixture of 1 liter of cold water and 1 kg of ice. The crude product was extracted with 3×500 ml of dichloromethane. The combined organic extract was washed by aqueous K2CO3 and then evaporated to dryness. Fractional rectification of the residue gave 64.9 g of yellowish oil which crystallizes at room temperature. On the evidence of NMR spectroscopy, this product includes ca. 90% of the target material. Further on, this product was dissolved in 180 ml of hot hexanes. Crystals precipitated from this solution at room temperature were collected, washed by 100 ml of cold hexanes, and dried in vacuum. This procedure gave 39.6 g (43%) of the analytically pure substituted indanone. was added for ca. 1 h at 50-55° C The crude product was extracted with 3×500 ml of dichloromethane The combined organic extract was washed by aqueous K2CO3 evaporated to dryness

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

Procedure: To an Eaton's reagent obtained from 110 g of P4O10 and 560 ml of methanesulfonic acid a mixture of 65.6 g (0.399 mol) of 1-tert-butyl-2-methoxybenzene and 43.0 g (0.50 mol) of methacrylic acid was added for ca. 1 h at 50-55° C. The resulting mixture was stirred for 1 h at this temperature, then cooled to room temperature, and poured on a mixture of 1 liter of cold water and 1 kg of ice. The crude product was extracted with 3×500 ml of dichloromethane. The combined organic extract was washed by aqueous K2CO3 and then evaporated to dryness. Fractional rectification of the residue gave 64.9 g of yellowish oil which crystallizes at room temperature. On the evidence of NMR spectroscopy, this product includes ca. 90% of the target material. Further on, this product was dissolved in 180 ml of hot hexanes. Crystals precipitated from this solution at room temperature were collected, washed by 100 ml of cold hexanes, and dried in vacuum. This procedure gave 39.6 g (43%) of the analytically pure substituted indanone. was added for ca. 1 h at 50-55° C The crude product was extracted with 3×500 ml of dichloromethane The combined organic extract was washed by aqueous K2CO3 evaporated to dryness

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

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To Iton reagent (obtained from 110 g of P4O10 and 560 ml of methanesulfonic acid at 110° C.) a mixture of 59.4 g (0.362 mol) of 1-tert-butyl-2-methoxybenzene and 51.5 g (0.402 mol) of 2-isobutylacrylic acid was added dropwise at vigorous stirring in such a rate to maintain temperature at 60±1° C. (for ca. 40 min). The resulting mixture was stirred for 40 min at 65° C., cooled to room temperature, and then poured on 1000 cm3 of ice with 1000 cm3 of water. The product was extracted by 3×500 ml of dichloromethane. The combined organic extract was washed by aqueous K2CO3, dried over Na2SO4 and then evaporated to dryness. Fractional rectification of the residue gave dark red oil, b.p. 165-174° C./5 mm Hg. This oil was recrystallized from 100 ml of hexanes. White crystals precipitated at 5° C. were collected, washed by 20 ml of cold hexanes, and dried in vacuum. Yield 24.9 g (25%) of the title product. was added dropwise The resulting mixture was stirred for 40 min at 65° C. cooled to room temperature The product was extracted by 3×500 ml of dichloromethane The combined organic extract was washed by aqueous K2CO3 dried over Na2SO4 evaporated to dryness Fractional rectification of the residue gave dark red oil, b.p. 165-174° C./5 mm Hg This oil was recrystallized from 100 ml of hexanes White crystals precipitated at 5° C. were collected washed by 20 ml of cold hexanes dried in vacuum

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

Procedure: The bis-indenyl ligand of formula (VIII) can be prepared following a synthetic strategy as outlined in Scheme 1. The key intermediate, the 6-tert-butyl-2-isobutyl-5-methoxyindan-1-one, was prepared by acylation of 2-tert-butylanisol with 2-isobutylacrylic acid followed by Nazarov cyclisation. Subsequent bromination, cross-coupling reaction with sodium tetraphenyl borate and reduction/dehydration of the obtained indanone gave the 5-tert-butyl-2-isobutyl-6-methoxy-7-phenyl-1H-indene. Reaction of its lithium salt with dichlorodimethylsilane produced the actual ligand bis(6-tert-butyl-2-isobutyl-5-methoxy-4-phenyl-1H-inden-1-yl)(dimethyl)silane in almost quantitative yield.

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

Procedure: A mixture of 1-tert-butyl-2-methoxybenzene (32.8 g, 0.2 mol) and methacrylic acid (21.5 g, 0.25 mol) was added at 60° C. to a well stirred Eaton reagent (55 g P2O5 and 280 ml of methanesulfonic acid). After 1 h of stirring the reaction mixture was cooled, poured into ice water, and extracted with benzene (3×200 ml). The combined organic layer was washed with water, aq. NaHCO3, dried over MgSO4, evaporated and distilled at 145-150° C./0.7 Torr. Yield 20 g (43%). was cooled extracted with benzene (3×200 ml) The combined organic layer was washed with water, aq. NaHCO3 dried over MgSO4 evaporated distilled at 145-150° C./0.7 Torr