Benzenesulfinyl Piperidine

InChl = 1/Cl 1H15NOS/C13-14(11-7-3-1 8-11)12-9-5-2-6-10-12/h 1,3-4,7-8H,2,5-6,9- 10H2 InChIKey = LBRJCAJLGAXDKP-UHFFFAOYAQ 

Solubility soluble in dichloromethane, diethyl ether, toluene, and most organic solvents. 

Analysis of Reagent Purity melting point, NMR spectrum. Preparative Methods a solution of PhSOCl (58.0 g, 0.365 mol) in anhydrous diethyl ether (200 mL) is slowly added to a cooled solution (5 °C) of piperidine (72 mL, 0.73 mmol) in anhydrous diethyl ether (200 mL). The reaction mixture is stirred at room temperature for 1 h, filtered, and then concentrated under reduced pressure. The solid residue is triturated with hexanes to give 1-benzenesulfinyl piperidine (53.4 g, 70%). 

Handling, Storage, and Precaution wdknovinioTAciiy. Should be used within a fumehood. 

The BSP/Tf20 reagent combination is not limited to the activation of ether protected thioglycosides. It also activates a 

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Benzenesulfinyl piperidine /2,4,6-tri-tertbutylpyrimidine /triflic anhydride (BSP/TTBP/Tf20) SEt, SPh [85]... 

To a solution of thioglycoside (1.0 equiv), 1-benzenesulfinyl piperidine (1.0 equiv), TTBP (2.0 equiv), and freshly activated 3 A powdered molecular sieves in dichloromethane (25.0 ml mmol-1) was added trifluoromethanesulfonic anhydride (1.1 equiv) at —60 °C under an argon atmosphere. The reaction mixture was stirred for 5 min, after that a solution of the glycosyl acceptor (1.5 equiv) in dichloromethane (4.0 ml mmol-1) was added. The reaction mixture was stirred at — 60 °C for 2 min, after that it was slowly warmed to room temperature and quenched by the addition of saturated aqueous NaHC03. The organic layer was washed with brine, dried (MgS04), filtered and the filtrate was concentrated to dryness. Purification of the crude product by column chromatography over silica gel afforded the product. 

Abbreviations Ac acetyl Bn benzyl BSP 1-benzenesulfinyl piperidine BTIB bis(trifluoroacetoxy)iodobenzene DAST (diethylamino)sulfur trifluoride DDQ 2,3-dichloro-5,6-dicyano-/)-benzoquinone DMDO dimethyldioxirane DMTSF dimethyl(methylthio)sulfonium tetrafluoroborate DMTST dimethyl(methylthio)sulfonium triflate DTBMP 2,6-Ai-tert-butyl-4-methylpyridine DTBP 2,6-di-tert-butylpyridine DTBPl 2,6-di-tert-butylpyridinium iodide FDCPT l-fluoro-2,6-dichloropyridinium triflate FTMPT l-fluoro-2,4,6-trimethylpyridinium triflate IDCP iodonium dicollidine perchlorate IDCT idonium dicollidine triflate LPTS 2,6-lutidinium p-toluenesulfonate LTMP lithium tetramethylpiperidide Me methyl MPBT S-(4-methoxyphenyl) benzenethiosulflnate NBS A-bromosuccinimide NIS A-iodosuccinimide NlSac A-iodosaccharin PPTS pyridinium p-toluenesulfonate TBPA tris(4-bromophenyl)ammoniumyl hexachloroantimonate Tf trifluoromethanesulfonyl TMTSB methyl-bis(methylthio)sulfonium hexachloroantimonate TMU tetramethylurea Tr trityl TTBP 2,4,6-tri-tert-butylpyrimidine. 

Crich, D, Smith, M, 1-Benzenesulfinyl piperidine/trifluoromethanesulfonic anhydride a potent combination of shelf-stable reagents for the low-temperature conversion of thioglycosides to glycosyl triflates and for the formation of diverse glycosidic hnkages, J. Am. Chem. Soc., 123, 9015-9020, 2001. 

Furthermore, these authors were also able to perform the -mannosylations with the thiogly-coside 35 under the action of PhSOTf [45] or 1-benzenesulfinyl piperidine (BSP)-Tf20 [46] (O Scheme 17). In the cases of both glycosyl sulfoxide and thioglycoside, protection of the 4- and 6-positions by a cyclic acetal is critical. The corresponding perbenzylated donors gave poor -selectivity [47]. 

Crich D, Banerjee A, Li W, Yao Q. Improved synthesis of 1-benzenesulfinyl piperidine and analogs for the activation of thioglycosides in conjunction with trifluoromethanesulfonic anhydride. J Carbohydr Chem 2005 24 415-424. 

To obtain more support for the remote participation of 3-0-acyl and 6-0-acetyl groups in mannosyl donors, Kim and co-workers carried out experiments to trap anomeric oxocarbenium ion intermediates by the intramolecular nucleophilic attack of the trichloroacetimidoyl group at the 0-3 position of mannosyl donors the activation of 72 with 1-benzenesulfinyl piperidine (BSP) and Tf20 afforded... 

Related Reagents. Dimethyl(methylthio)sulfonium Trifluoromethanesulfonate (DMTST) 7V-Iodosuccinimide W Iodosaccharin 1-Benzenesulfinyl Piperidine Diphenyl Sulfoxide. 

Related Reagents. 1-Benzenesulfinyl Piperidine Methoxy-phenyl Benzenethiosulfinate Benzothianthrene Oxide W Iodo-succinitnide Dimethyl(methylthio)sulfonium Tetrafluoroborate. 

This limitation of activation has been overcome by the combination of 1-benzenesulfinyl piperidine (BSP) and Tf20. ... 

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