4,5-二溴-2-呋喃甲醛

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A degassed mixture of the product of Step 3 (6.6 g, 26.0 mmol), 1-methoxyimino-indan-5-boronic acid (5.3 g, 26.0 mmol) and potasium carbonate (28 g, 202 mmol) in ethylene glycol dimethyl ether (150 ml) and water (75 ml) was treated with bis(triphenylphosphine) palladium (II) chloride (1.05 g, 1.5 mmol), then heated under reflux for 6 hours. After cooling to room temperature, the mixture was filtered through celite and the filtrate diluted with water and ethyl acetate. The organic phase was separated, washed with water and brine, dried, concentrated in vacuo and the residue purified by silica gel chromatography eluting with dichloromethane to give the title compound (3.06 g, 35%); MS(ES+) m/e 334/336 [M+H]+. heated under reflux for 6 hours the mixture was filtered through celite the filtrate diluted with water and ethyl acetate The organic phase was separated washed with water and brine dried concentrated in vacuo the residue purified by silica gel chromatography eluting with dichloromethane

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A degassed mixture of the product of Step 3 (6.6 g, 26.0 mmol), 1-methoxyimino-indan-5-boronic acid (5.3 g, 26.0 mmol) and potasium carbonate (28 g, 202 mmol) in ethylene glycol dimethyl ether (150 ml) and water (75 ml) was treated with bis(triphenylphosphine) palladium (II) chloride (1.05 g, 1.5 mmol), then heated under reflux for 6 hours. After cooling to room temperature, the mixture was filtered through celite and the filtrate diluted with water and ethyl acetate. The organic phase was separated, washed with water and brine, dried, concentrated in vacuo and the residue purified by silica gel chromatography eluting with dichloromethane to give the title compound (3.06 g, 35%); MS(ES+) m/e 334/336 [M+H]+. heated under reflux for 6 hours the mixture was filtered through celite the filtrate diluted with water and ethyl acetate The organic phase was separated washed with water and brine dried concentrated in vacuo the residue purified by silica gel chromatography eluting with dichloromethane

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Diisobutylaluminum hydride (80 ml, 1M solution in toluene) was added to a solution of the product from Step 2 (20 g, 63.4 mmol) in tetrahydrofuran (160 ml) at −78° C. The mixture was stirred at −78° C. for 1.5 hours and was then quenched with a saturated aqueous solution of ammonium chloride (40 ml). The reaction was allowed to warm to room temperature, diluted with ethyl acetate and 5M hydrochloric acid (20 ml) and stirred for 30 minutes. The organic layer was separated, washed twice with water and then brine, dried and concentrated in vacuo to yield the title compound (12.9 g, 81%); 1H NMR (CDCl3) 9.52 (1H, s), 7.21 (1H, s). was then quenched with a saturated aqueous solution of ammonium chloride (40 ml) to warm to room temperature diluted with ethyl acetate and 5M hydrochloric acid (20 ml) stirred for 30 minutes The organic layer was separated washed twice with water brine, dried concentrated in vacuo

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Diisobutylaluminum hydride (80 ml, 1M solution in toluene) was added to a solution of the product from Step 2 (20 g, 63.4 mmol) in tetrahydrofuran (160 ml) at −78° C. The mixture was stirred at −78° C. for 1.5 hours and was then quenched with a saturated aqueous solution of ammonium chloride (40 ml). The reaction was allowed to warm to room temperature, diluted with ethyl acetate and 5M hydrochloric acid (20 ml) and stirred for 30 minutes. The organic layer was separated, washed twice with water and then brine, dried and concentrated in vacuo to yield the title compound (12.9 g, 81%); 1H NMR (CDCl3) 9.52 (1H, s), 7.21 (1H, s). was then quenched with a saturated aqueous solution of ammonium chloride (40 ml) to warm to room temperature diluted with ethyl acetate and 5M hydrochloric acid (20 ml) stirred for 30 minutes The organic layer was separated washed twice with water brine, dried concentrated in vacuo

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A degassed mixture of the product of Step 3 (6.6 g, 26.0 mmol), 1-methoxyimino-indan-5-boronic acid (5.3 g, 26.0 mmol) and potasium carbonate (28 g, 202 mmol) in ethylene glycol dimethyl ether (150 ml) and water (75 ml) was treated with bis(triphenylphosphine) palladium (II) chloride (1.05 g, 1.5 mmol), then heated under reflux for 6 hours. After cooling to room temperature, the mixture was filtered through celite and the filtrate diluted with water and ethyl acetate. The organic phase was separated, washed with water and brine, dried, concentrated in vacuo and the residue purified by silica gel chromatography eluting with dichloromethane to give the title compound (3.06 g, 35%); MS(ES+) m/e 334/336 [M+H]+. heated under reflux for 6 hours the mixture was filtered through celite the filtrate diluted with water and ethyl acetate The organic phase was separated washed with water and brine dried concentrated in vacuo the residue purified by silica gel chromatography eluting with dichloromethane

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Diisobutylaluminum hydride (80 ml, 1M solution in toluene) was added to a solution of the product from Step 2 (20 g, 63.4 mmol) in tetrahydrofuran (160 ml) at −78° C. The mixture was stirred at −78° C. for 1.5 hours and was then quenched with a saturated aqueous solution of ammonium chloride (40 ml). The reaction was allowed to warm to room temperature, diluted with ethyl acetate and 5M hydrochloric acid (20 ml) and stirred for 30 minutes. The organic layer was separated, washed twice with water and then brine, dried and concentrated in vacuo to yield the title compound (12.9 g, 81%); 1H NMR (CDCl3) 9.52 (1H, s), 7.21 (1H, s). was then quenched with a saturated aqueous solution of ammonium chloride (40 ml) to warm to room temperature diluted with ethyl acetate and 5M hydrochloric acid (20 ml) stirred for 30 minutes The organic layer was separated washed twice with water brine, dried concentrated in vacuo

实验步骤: 投料: 取100ml三口瓶，称取AlCl3（1eq）， 置换氮气，将原料SM1溶于超干DCM，冰浴搅拌下缓慢滴加至AlCl3中，缓慢滴加溴素，加毕RT搅拌过夜。\n监测: TLC(PE:EA=10:1)没有发现新点, 都是原料。

实验步骤: 投料: 取50ml三口瓶，分别加入SM1，CuI, PdCl2（PPh3）2，加入超干THF溶解，加三乙胺和SM2，置换氮气，RT搅拌过夜。\n监测: TLC（PE:EA=10:1）显示原料消失，生成一个极性略大的主点（Rf=0.4）。\n纯化: 将体系直接浓缩至干，硅胶柱层析，PE/EA洗脱，5%EA出产物，收集浓缩得黄色液体纯品8.0g。HNMR（280625-3-FD）显示大部分为一个炔基产物，有少量杂质。

实验步骤: 投料: 取50ml三口瓶，分别加入SM1，CuI, PdCl2（PPh3）2，加入超干THF溶解，加三乙胺和SM2，置换氮气，RT搅拌过夜。\n监测: TLC（PE:EA=10:1）显示原料消失，生成一个极性略大的主点（Rf=0.4）。\n纯化: 将体系直接浓缩至干，硅胶柱层析，PE/EA洗脱，5%EA出产物，收集浓缩得黄色液体纯品。HNMR（280625-3-3）显示为接两个炔和接一个炔的混合物。

实验步骤: 投料: 取100ml三口瓶，称取AlCl3（1eq）， 置换氮气，将原料SM1溶于超干DCM，冰浴搅拌下缓慢滴加至AlCl3中，缓慢滴加溴素（溴素在最下层，棕黑色液体，上层橙色液体为水），加毕RT搅拌过夜。\n监测: GCMS（280625-1-FD）确定反应完全，主峰为产物（M=254），TLC（PE：EA=10:1）原料消失，生成一个极性变小的新点（Rf=0.6）。\n后处理: 将反应液缓慢倒入冰水中，向冰浴中加入饱和碳酸钠溶液，调节PH至弱碱性（PH=7-8），搅拌1h。DCM萃取三次，合并有机相，无水硫酸钠干燥，浓缩得产物粗品。\n纯化: 硅胶柱层析，PE：EA=6%EA出产物峰，收集浓缩得棕色油状物（收率63%）。

实验步骤: 投料: 取100ml三口瓶，称取AlCl3（1eq）， 置换氮气，将原料SM1溶于超干DCM，冰浴搅拌下缓慢滴加至AlCl3中，缓慢滴加溴素（溴素在最下层，棕黑色液体，上层橙色液体为水），加毕RT搅拌过夜。\n纯化: 硅胶柱层析，PE：EA=6%EA出产物峰，收集浓缩得棕色油状物（收率63%）。\n后处理: 将反应液缓慢倒入冰水中，向冰浴中加入饱和碳酸钠溶液，调节PH至弱碱性（PH=7-8），搅拌1h。DCM萃取三次，合并有机相，无水硫酸钠干燥，浓缩得产物粗品。\n监测: GCMS（280625-1-FD）确定反应完全，主峰为产物（M=254），TLC（PE：EA=10:1）原料消失，生成一个极性变小的新点（Rf=0.6）。