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copper(II) sulfate; In dichloromethane; at 20℃; for 17h;
Intermediate 44: (S)-(3-Methylpyridin-2-yl)(4-(trifluoromethyl)phenyl)- methanamine hydrochlorid Step 1. (S^-l-Methyl-N-iiS-methylpyridin-l-ylJmethyleneipropane-l- sulflnamideTo a solution of <strong>[55589-47-4]3-methyl-2-pyridinecarboxaldehyde</strong> (3.243 g, 26.8 mmol) in DCM (18 mL) was added (S)-2-methylpropane-2-sulfinamide (6.55 g, 54.0 mmol) and copper(II) sulfate (8.72 g, 54.6 mmol). The suspension was stirred at rt for 17 hours, filtered, and the solid was washed with DCM (2 x 35 mL). The filtrates were concentrated, and the resulting product was purified by silica gel flash column chromatography (using a 80G ISCO cartridge) and eluted using DCM / MeOH gradient to yield the desired product (S,E)-2-methyl-N-((3- methylpyridin-2-yl)methylene)propane-2-sulfinamide as a yellow solid.
980 mg
With copper(II) sulfate; In dichloromethane; at 20℃; for 2h;
3-Methyl-2-pyridinecarbaldehyde (0.750 mL, 6.69 mmol, Sigma- Aldrich, St. Louis, MO) was added to a solution of (S)-2-methylpropane-2- sulfmamide (1.14 g, 9.36 mmol, AK Scientific, Mountain View, CA) and copper(II) sulfate (3.20 g, 20.1 mmol) in DCM (50 mL) and the mixture was stirred at room temperature for 2 h. The mixture was filtered, the filter residue was washed with DCM (30 mL), and the combined filtrate and washing were concentrated under reduced pressure. The residue was purified by flash chromatography (100 g of silica gel, 33percent EtOAc/hexanes) to afford (S)-N-((1E)- (3-methyl-2-pyridinyl)methylidene)-2-methyl-2-propanesulfinamide (980 mg) as a light-yellow solid.
With titanium(IV) isopropylate; In tetrahydrofuran; at 90℃; for 16h;
The mixture of l -(3-isopropylphenyl)ethanone (5.8 g, 0.036 mol), (S)-2- methylpropane-2-sulfinamide (5.2 g, 0.043 mol) and Ti(OiPr)4 in THF was stirred at 90 C for 16 hours. Then the mixture was poured to water and the solid was filtered, the filtrate was partitioned between EtOAc and water. The layers were separated and the organic layer was washed with water, brine, dried over a?S04, and concentrated. The residue was pui'ified by column chromatography to give the titled compound. LC-MS: mix 266(M+H
With titanium(IV) isopropylate; In tetrahydrofuran; at 90℃; for 16h;
The mixture of l~(3-isopropyJphenyl)ethanone (5.8 g, 0.036 mol), (S)-2- methylpropane-2-sulfinamide (5.2 g, 0.043 mol) and Ti(OiPr) in THF was stirred at 90 UC for 16 hours. Then the mixture was poured to water and the solid was filtered, the filtrate was partitioned between EtOAc and water. The layers were separated and the organic layer was washed with water, brine, dried over Na2S0 , and concentrated. The residue was purified by column chromatography to give the titled compound. LC-MS: m/z 266(M+H)+
With titanium(IV) tetraethanolate; In tetrahydrofuran; at 20℃; for 18h;
a) To a solution of 4'-chloro-2'-fluoroacetopheiioiie (7.5 g, 43.6 mmol) and (?)-(-)- 1- butanesulfinamide (5.3 g, 44.0 mmol) in anhydrous tetrahydrofuran (THF, 125 mL) was added titanium(IV) ethoxide (Ti(OEt)4, 24.8 g, 109.0 mmol). The reaction mixture was stirred at room temperature for 18 h. The mixture was poured into a solution of brine, and the mixture was stirred at room temperature for 1 h. The solution was filtered, and the phases were separated. The organic layer was further washed with brine. The organic layer was then dried with anhydrous sodium sulfate (Na2S04), filtered, and concentrated in vacuo. The crude material was used without further purification (7.9 g, 28.7 mmol, 66%).
(S,E)-N-(1-(3,5-dichlorophenyl)ethylidene)-2-methylpropane-2-sulfinamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
With titanium(IV) isopropylate; In tetrahydrofuran; at 80℃; for 16h;
Tetraisopropoxytitanium (6.14 g, 21.2 mmol) was added to a solution of 3, 5-dichlorophenyl ethanone (1.0 g, 5.3 mmol) and (S) -2-methylpropane-2-sulfinamide (1.28 g, 10.6 mmol) in dry THF (20 mL) . After stirring at 80 for 16 h, ethyl acetate (15 mL) and brine was added to quench the reaction. The white precipitate was filtered and the filtrate was concentrated and purified by silica gel chromatography (eluting with ethyl acetate/petroleum ether 1/10) to give the target compound as a yellow solid (1.24 g, 80) . LCMS (ESI) : m/z 292.0 [M+H]+.
(S,E)-N-(2-fluoro-5-(trifluoromethoxy)benzylidene)-2-methylpropane-2-sulfinamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
91%
With titanium(IV)isopropoxide; In tetrahydrofuran; at 20℃; for 72h;
Titanium(IV) isopropoxide (5.69 mL, 19.22 mmol) was added to a THF (20 mL) solution of <strong>[886497-81-0]2-fluoro-5-(trifluoromethoxy)benzaldehyde</strong> (2.0 g, 9.61 mmol) and (S)-(10 )-2-methyl-2-propanesulfinamide (1.165 g, 9.61 mmol) at ft and stirred for 72 h. Thereaction mixture was quenched by adding brine (10 mL) and hexanes (10 mL) at 0 C.The mixture was filtered through a pad of celite, and the pad was rinsed with ethyl acetate(2 x 10 mL). The combined organic solutions were dried over sodium sulfate, filtered andconcentrated under reduced pressure to give crude product which was purified on a silicagel column with Hexanes/EtOAc (100/0 to 50/50) to give (S,E)-N-(2-fluoro-5-(trifluoromethoxy)benzylidene)-2-methylpropane-2-sulfinamide (2.827 g, 8.73 mmol, 91%yield).MS ESI m/z 312.0 (M+H)
(S,E)-N-((2-bromopyridin-4-yl)methylene)-2-methylpropane-2-sulfinamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With titanium(IV) tetraethanolate; In tetrahydrofuran; at 35℃; for 1h;Inert atmosphere;
To a mixture of 2-bromoisonicotinaldehyde (68.0 g, 365 mmol) and compound (S)-2-methylpropane-2-sulfinamide (48.7 g, 402 mmol) in THF (400 mL) was added Ti(OEt)4 (125 g, 548 mmol, 113 mL) in one portion at 20 C. under N2. The mixture was stirred at 35 C. for 1 h. Water (200 mL) and EtOAc (200 mL) was added into the mixture, and stirred for 5 min. The mixture was filtered, and the filtered cake was washed with EtOAc (200 mL). The combined organic layers were washed with water (200 mL) and brine (200 mL), dried over anhydrous Na2SO4 and concentrated in vacuoto give compound (S,E)-N-((2-bromopyridin-4-yl)methylene)-2-methylpropane-2-sulfinamide (90.0 g, crude) as a yellow solid.
(S)-N-((4-chloro-3-fluoropyridin-2-yl)methylene)-2-methylpropane-2-sulfinamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With caesium carbonate; In dichloromethane; at 20℃; for 1h;
To a solution of <strong>[1260878-78-1]4-chloro-3-fluoropicolinaldehyde</strong> (220a) (6.73 g, 42.2 mmol; CASNo. 1260878-78-1) and Cs2C03 (27.5 g, 84 mmol) in DCM (350 mL) was added (S)-2- methylpropane-2-sulfmamide (5.88 g, 48.5 mmol) and stirred at rt for 1 h. The reaction mixture was diluted with DCM and washed with brine (3 x 200 mL). The organic layer was dried, filtered and concentrated in vacuo to afford (S)-N-((4-chloro-3 -fluoropyri din-2 - yl)methylene)-2-methylpropane-2-sulfmamide (220b) (11.08 g,l00 % yield) which was used in the next reaction without further purification; 'H NMR (300 MHz, DMSO-rL) d 8.59 (d, J = 5.1Hz, 1H), 8.56 (s, 1H), 7.97 (dd, J = 5.6, 5.0 Hz, 1H), 1.21 (s, 9H).
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