content_image/898641.jpg content_image/898644.jpg
stirred for aging at room temperature for 6 days. The reaction solution was quenched with 20 g of water, com› bined with 0.79 g of pyridine, and stirred at room tempera› ture for 30 minutes. An organic layer was taken out, washed twice with 15 g of water, combined with 2.79 g ofbenzyl- trimethylammonium chloride and 30 g of water, and stirred for 1 hour. The organic layer was taken out and washed 3 times with 15 g of water, followed by vacuum concentration to remove dichloromethane. Steps of adding 30 g of diiso- propyl ether to the concentrate, stirring for 5 minutes, and removing a supernatant were repeated 3 times. Subsequent vacuum concentration left 2.65 g of the desired Intermediate 

$^{19}$F-NMR (500 MHz, DMSO-d$_{4}$ ): o=-78.8 (3F, s) ppm 

MALDI-TOF-MS: 

Positive M+ 263 (corresponding to C$_{18}$H$_{15}$S+) 

Negative M- 364 (corresponding to C$_{8}$H$_{9}$O 2 -OSO$_{1}$N› SO2CF3) 

PAG-3 was synthesized according to the following scheme. 

## Synthesis Example 3 

## Synthesis of PAG-3 

<img src='content_image/898641.jpg'>

2 as oily product (yield 51%). Analytic results by $^{1}$H- and $^{19}$F-NMR spectroscopy are shown below. 

$^{1}$H-NMR (500 MHz, DMSO-d$_{6}$ ): 

o=l.55 (2H, m), 1.83 (lH, m), 1.98 (lH, m), 2.49 (le, m), 2.55 (lH, m), 3.00 (9H, s), 3.18 (lH, m), 4.20 (lH, s), 4.50 (2H, s), 4.67 (lH, d), 7.51-7.54 (5H, m) ppm 

$^{19}$F-NMR (500 MHz, DMSO-d$_{6}$ ): o=78.9 (3F, s) ppm 

In a mixture of 20 g of dichloromethane and 10 g of water, 2.64 g of Intermediate 2 and 1.92 g of triphenylsulfonium methylsulfate were dissolved, followed by stirring at room temperature for 30 minutes. An organic layer was taken out and washed 3 times with 10 g of water and 3 times with a mixture of 10 g water and 1 g methanol. The organic layer was concentrated in vacuum, combined with 30 g of diiso› propyl ether, and stirred for 30 minutes for crystallization. Crystals were collected by filtration, washed twice with 20 g of diisopropyl ether, and dried in vacuum, obtaining 2.53 g of the desired PAG-2 as white solid product (yield 79%). Analytic results by $^{1}$H-NMR, $^{19}$F-NMR and MALDI-TOF› MS are shown below. 

$^{1}$H-NMR (500 MHz, DMSO-d$_{6}$ ): 

o=l .55 (2H, m), 1.82 (lH, m), 2.00 (lH, m), 2.49 (lH, m), 65 2.55 (lH, d), 3.19 (lH, m), 4.20 (lH, s), 4.67 (lH, d), 7.76-7.88 (15H, m) ppm 

## Synthesis Example 2-2 

## Synthesis of PAG-2 

<img src='content_image/898644.jpg'>

Under ice cooling, a solution of 1.64 g of trifluorometh- anesulfonamide and 2.61 g of pyridine in 5 g of acetonitrile was added dropwise to a solution of 1 .48 g of sulfuryl chloride in 5 g of acetonitrile. The solution was stirred still under ice cooling for 10 minutes and then at room tempera› ture for 5.5 hours. Under ice cooling, a solution of 1.52 g of 2-adamantanol and 0.06 g ofN,N-dimethylaminopyridine in 5 g of acetonitrile and 5 g of dichloromethane was added dropwise to the reaction solution. The solution was stirred at 50° C. for 76 hours for aging. The reaction solution was quenched with 0.5 g of methanol and stirred at 50° C. for a further 15 hours. Then 5 g of water and 0.5 g of pyridine were added to the solution, which was stirred for 1 hour. Further, 40 g of MIBK and 20 g of water were added to the solution, from which an organic layer was taken out. The organic layer was washed with 20 g of water, combined with 2.04 g of benzyltrimethylammonium chloride and 20 g of water, and stirred for 1 hour. The organic layer was taken out and washed twice with 20 g of water, twice with a mixture of 20 g water and 5 g methanol, and twice with 20 g of water, followed by vacuum concentration to remove the solvent. Steps of adding 30 g of diisopropyl ether to the concentrate, 

## Synthesis Example 3-1 

## Synthesis of Intermediate 3 

