86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 4℃; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile at 4℃; for 0.916667h; Inert atmosphere;
Stage #3: With pyridine In acetonitrile at 20℃; for 0.25h; Inert atmosphere; |
|
86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 4℃; for 0.75h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile at 4℃; for 0.916667h; Inert atmosphere; |
|
86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 4℃; for 0.75h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile at 4℃; for 0.916667h; Inert atmosphere; |
|
86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 4℃; for 0.75h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene With pyridine In acetonitrile at 4 - 20℃; for 0.916667h; Inert atmosphere; |
|
86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 4℃; for 0.75h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile for 0.916667h; Inert atmosphere;
Stage #3: With pyridine In acetonitrile at 23℃; for 0.25h; Inert atmosphere; |
|
86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile for 0.75h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile for 0.916667h; Inert atmosphere; |
|
86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 0℃; for 0.75h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene With pyridine In acetonitrile for 1.16667h; Inert atmosphere; |
|
86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 4℃; for 0.75h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile at 4℃; for 0.916667h; Inert atmosphere;
Stage #3: With pyridine In acetonitrile for 0.25h; Inert atmosphere; |
1-[(Triiso-propylsilyl)ethynyl]-1,2-benziodoxol-3(1H)-one (TIPS-EBX, 4d)
Following a reported procedure,9 2-iodosylbenzoic acid (9) (21.7 g, 82.0 mmol, 1.0 equiv) was charged inoven-dried three-neck 1L flask equipped with a magnetic stirrer. After 3 vacuum/nitrogen cycles, anhydrousacetonitrile (500 mL) was added via cannula and cooled to 4 °C. Trimethylsilyltriflate (16.4 mL, 90.0 mmol,1.1 equiv) was added dropwise via a dropping funnel over 30 min (no temperature increase was observed).After 15 min, (trimethylsilyl)(triisopropylsilyl)acetylene (11) (23.0 g, 90.0 mmol, 1.1 equiv) was added viacanula over 15 min (no temperature increase was observed). After 30 min, the suspension became an orangesolution. After 10 min, pyridine (7.0 mL, 90 mmol, 1.1 equiv) was added via syringe. After 15 min, thereaction mixture was transferred in a one-neck 1L flask and reduced under vacuum until a solid wasobtained. The solid was dissolved in DCM (200 mL) and transferred in a 1L separatory funnel. The organiclayer was added and washed with aq. 1 M HCl (200 mL) and the aqueous layer was extracted with CH2Cl2(200 mL). The organic layers were combined, washed with a saturated solution of NaHCO3 (2 x 200 mL),dried over MgSO4, filtered and the solvent was evaporated under reduced pressure. Recrystallization from acetonitrile (ca 120 mL) afforded 4d (30.1 g, 70.2 mmol, 86%) as colorless cristals. |
86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 0℃; for 0.75h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In pyridine; acetonitrile at 0 - 20℃; Inert atmosphere; |
|
86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 0℃; for 0.75h;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene for 0.916667h; |
|
86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 0℃; for 0.25h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile for 0.75h; Inert atmosphere;
Stage #3: With pyridine In acetonitrile for 0.166667h; Inert atmosphere; |
1-[(Triisopropylsilyl)ethynyl]-1,2-benziodoxol-3(1H)-one
Following a reported procedure,3 2-iodosylbenzoic acid (7, 21.7 g, 82.0 mmol, 1.00 equiv) wascharged in an oven-dried three-necked 1L flask equipped with a magnetic stirrer. After 3vacuum/nitrogen cycles, anhydrous acetonitrile (500 mL) was added via canula and cooled to 0°C. Trimethylsilyltriflate (16.4 mL, 90.0 mmol, 1.10 equiv) was added dropwise via a droppingfunnel over 30 min (no temperature increase was observed). After 15 min,(trimethylsilyl)(triisopropylsilyl)acetylene (9, 23.0 g, 90.0 mmol, 1.10 equiv) was added viacanula over 15 min (no temperature increase was observed). After 30 min, the suspension becamean orange solution. After 10 min, pyridine (7.0 mL, 90 mmol, 1.1 equiv) was added via syringe.After 15 min, the reaction mixture was transferred in a one-necked 1L flask and the volumereduced under vacuum until a solid was obtained. The solid was dissolved in CH2Cl2 (200 mL)and transferred in a 1L separatory funnel. The organic layer was washed with 1 M HCl (200 mL)and the aqueous layer was back-extracted with CH2Cl2 (200 mL). The organic layers werecombined, washed with a saturated solution of NaHCO3 (2 x 200 mL), dried over MgSO4,filtered and the solvent was evaporated under reduced pressure. |
86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 0℃; for 0.25h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile for 0.666667h; Inert atmosphere;
Stage #3: With pyridine In acetonitrile for 0.25h; Inert atmosphere; |
|
86% |
With pyridine; trimethylsilyl trifluoromethanesulfonate In acetonitrile at 0 - 20℃; Inert atmosphere; |
|
86% |
With pyridine; trimethylsilyl trifluoromethanesulfonate In acetonitrile at 20℃; |
|
86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile for 0.25h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile for 0.5h; Inert atmosphere; |
|
86% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile for 0.75h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile at 20℃; for 0.5h; Inert atmosphere; |
|
85% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 4℃; for 0.5h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In aceronitrile for 0.75h; Inert atmosphere;
Stage #3: With pyridine In acetonitrile for 0.333333h; Inert atmosphere; |
|
85% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one In acetonitrile for 0.5h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile for 0.75h; Inert atmosphere; |
|
85% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With 2-Iodobenzoic acid In acetonitrile at 4℃; for 0.5h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile for 0.75h; Inert atmosphere;
Stage #3: With pyridine In acetonitrile for 0.333333h; Inert atmosphere; |
|
85% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 0℃; for 0.25h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile for 0.5h;
Stage #3: With pyridine In acetonitrile for 0.25h; |
1.c C, for the preparation of 1 - [(three different propyl silicon-based) ethynyl] - 1, 2 - benzenesulfonyl -3 (1H) - one
Under a N2 protection, a dry 100 mL flask equipped with a magnetic stirrer was charged with 1- (hydroxy) -1,2-phenyl iodide(2H) -one (2.64 g, 10 mmol) and anhydrous CH3CN (45 mL) were cooled to 0 ° C and then trimethylsilyl trifluoromethanesulfonate (2 mL) was added dropwise to the flask and stirred for 15 min, To the flask was added trimethylsilyl (triisopropylsilyl) acetylene (2.8 g, 11 mmol) and stirred for 30 min. Then, pyridine (0.88 mL) was added dropwise to the flask and stirred for 15 min. The reaction was transferred to 100 mL The organic phase was washed with IM HCl (25 mL) and the aqueous phase was washed with dichloromethane (25 mL). The organic phases were combined and washed with saturated NaHCO3 (2 * 25 mL), dried, filtered, concentrated and recrystallized from acetonitrile (15 mL) to give 3.62 g of white crystals in 85% yield, |
84% |
With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 0℃; for 0.916667h; Inert atmosphere; |
|
83% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one; 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 20℃; for 0.25h; Inert atmosphere;
Stage #2: With pyridine In acetonitrile at 20℃; for 0.166667h; Inert atmosphere; |
|
83% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile for 0.25h; Inert atmosphere;
Stage #3: With pyridine In acetonitrile for 0.166667h; Inert atmosphere; |
|
83% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 20℃; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile at 20℃; Inert atmosphere;
Stage #3: With pyridine In acetonitrile at 20℃; Inert atmosphere; |
|
83% |
With pyridine; trimethylsilyl trifluoromethanesulfonate In acetonitrile for 0.25h; Inert atmosphere; |
|
83% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 0℃; for 0.75h;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile at 0℃; for 0.75h;
Stage #3: With pyridine In acetonitrile for 0.25h; |
|
83% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one; 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene With trimethylsilyl trifluoromethanesulfonate In acetonitrile for 0.25h; Inert atmosphere;
Stage #2: With pyridine In acetonitrile for 0.166667h; Inert atmosphere; |
|
83% |
With pyridine; trimethylsilyl trifluoromethanesulfonate In acetonitrile at 20℃; |
|
80% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In dichloromethane at 25℃; for 1.5h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In dichloromethane at 20℃; for 6h; Inert atmosphere; |
|
80% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In dichloromethane at 20℃; for 1.5h;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In dichloromethane at 20℃; for 6h; |
|
75% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 0 - 20℃;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile at 20℃;
Stage #3: With pyridine In acetonitrile at 20℃; |
1-[(Triisopropylsilyl)ethynyl]-1,2-benziodoxol-3(1H)-one (1l)
Following a reported procedure,15 a cooled solution of trimethylsilyl trifluoromethanesulfonate (TMSOTf,19.9 mL, 110 mmol, 1.10 equiv.) was added dropwise to a stirred suspension of 2-iodosylbenzoic acid(65) (26.4 g, 100.0 mmol, 1.00 equiv.) in acetonitrile (350 mL) at 0 °C. The mixture was then allowed towarm to room temperature and was stirred for 15 minutes. Then trimethylsilyl(triisopropylsilyl)acetylene(59) (28.0 g, 110 mmol, 1.10 equiv.) was added dropwise to the reaction mixture. After 30 minutes,pyridine (9.8 mL, 122 mmol, 1.10 equiv.) was added dropwise and, 15 minutes later, the reaction mixturewas concentrated under reduced pressure. The collected solid was dissolved in dichloromethane (250mL) and washed with a 1.0 N aqueous hydrochloric acid (150 mL). The aqueous layer was extractedwith dichloromethane (250 mL), then the combined organic layers were washed with a saturatedaqueous sodium bicarbonate (2 x 250 mL), dried over magnesium sulfate, filtered and concentrated invacuo. The resulting solid was then recrystallized from acetonitrile and washed with hexanes (2 x 40mL) to yield pure TIPS-EBX (1l) (32.1 g, 74.9 mmol, 75% yield) as white crystals. |
71.7% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 4℃; for 0.75h;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile at 4℃; for 0.916667h;
Stage #3: With pyridine In acetonitrile at 20℃; for 0.25h; |
|
71% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one In acetonitrile at 0℃; for 0.25h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene With pyridine In acetonitrile for 0.25h; Inert atmosphere; |
|
71% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 0℃; for 0.25h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile for 0.5h; Inert atmosphere;
Stage #3: With pyridine In acetonitrile at 20℃; for 0.25h; Inert atmosphere; |
|
70% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 25℃; for 0.25h;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile at 25℃; for 0.333333h; |
|
64% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate at 4℃; for 0.25h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene at 20℃; for 0.583333h; Inert atmosphere;
Stage #3: With pyridine at 20℃; for 0.333333h; Inert atmosphere; |
|
64% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 4℃; for 0.25h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene With pyridine In acetonitrile at 20℃; for 0.916667h; Inert atmosphere; |
|
55% |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 20℃; for 0.5h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile at 20℃; for 0.5h; Inert atmosphere;
Stage #3: With pyridine In acetonitrile for 0.25h; Inert atmosphere; |
|
|
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile for 0.25h;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile for 0.333333h;
Stage #3: With pyridine In acetonitrile |
1-[(triisopropylsilyl)ethynyl]-1,2-benziodoxol-3(1H)-one (2d)
According a slight modifiedreported procedure,3 to a stirred solution of 2-iodosylbenzoic (8) acid 1 (1 eq.) in dry MeCN was addedtrimethylsilyl triflate (1.1 eq). After stirring 15 min the triisopropyl((trimethylsilyl)ethynyl)silane6 (1.1 eq.) was added. The reactionmixture was stirred for next 20 min, and then pyridine (1.1 eq.) was added andthe solvent was evaporated. The residual crude oil was washed with water andsaturated solution of NaHCO3. Organic layer was dried over MgSO4,filtered and evaporated affording a white, solid product (2d), which was recrystallized from acetonitrile. |
|
With pyridine; trimethylsilyl trifluoromethanesulfonate In acetonitrile at 4 - 20℃; for 1.91667h; |
Preparation of Reagents 1-[(Triiso-propylsilyl)ethynyl]-1,2-benziodoxol-3(1H)-one (TIPS-EBX, 2a)
Following a reported procedure, 2-iodosylbenzoic acid (21.7 g, 82.0 mmol, 1.0 equiv) was charged in oven-dried three-neck 1L flask equipped with a magnetic stirred. After 3 vacuum/nitrogen cycles, anhydrous acetonitrile (500 mL) was added via canula and cooled to 4 °C. Trimethylsilyltriflate (16.4 mL, 90.0 mmol, 1.1 equiv) was added dropwise via a dropping funnel over 30 min (no temperature increase was observed). After 15 min, (trimethylsilyl)(triisopropylsilyl)acetylene (23.0 g, 90.0 mmol, 1.1 equiv) was added via canula over 15 min (no temperature increase was observed). After 30 min, the suspension became an orange solution. After 10 min, pyridine (7.0 mL, 90 mmol, 1.1 equiv) was added via syringe. After 15 min, the reaction mixture was transferred in a one-neck 1L flask and reduced under vacuum until a solid was obtained. The solid was dissolved in CH2Cl2(200 mL) and transferred in a 1L separatory funnel. The organic layer was added and washed with 1 M HCl (200 mL) and the aqueous layer was extracted with CH2Cl2(200 mL). The organic layers were combined, washed with a saturated solution of NaHCO3 (2 x 200 mL), dried over MgSO4, filtered and the solvent was evaporated under reduced pressure. Recrystallization from acetonitrile (120 mL) afforded the product as colorless cristals. 1H NMR (400 MHz, CDCl3) δ 8.42-8.40 (m, 1H),8.30-8.28 (m, 1H), 7.77-7.74 (m, 2H), 1.15-1.14 (m, 21H). 13C NMR(100 MHz, CDCl3) δ 166.51, 134.85, 132.64, 131.71, 131.56, 126.18,115.75, 114.43, 64.87, 18.64, 11.33. HRMS (ESI) calcd for C18H26IO2Si+[M + H]+ : 429.0741, found : 429.0741. |
|
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In dichloromethane at 25℃; for 1h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In dichloromethane at 25℃; for 6h; Inert atmosphere; |
|
|
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In dichloromethane at 20℃; for 1h; Inert atmosphere;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In dichloromethane at 20℃; for 6h; Inert atmosphere;
Stage #3: With sodium hydrogencarbonate In dichloromethane for 0.5h; Inert atmosphere; |
|
|
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 20℃;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile at 20℃; for 6h; |
|
32.1 g |
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In acetonitrile at 0 - 20℃;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In acetonitrile at 20℃;
Stage #3: With pyridine In acetonitrile at 20℃; |
|
|
Stage #1: 1-hydroxy-1,2-benzodioxol-3-(1H)-one With trimethylsilyl trifluoromethanesulfonate In dichloromethane at 20℃; for 1h;
Stage #2: 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene In dichloromethane at 20℃; for 6h; |
|