Publications by authors named "Keisuke Shiraishi"

To investigate the possible interplanetary transfer of life, numerous exposure experiments have been carried out on various microbes in space since the 1960s. In the Tanpopo mission, we have proposed to carry out experiments on capture and space exposure of microbes at the Exposure Facility of the Japanese Experimental Module of the International Space Station (ISS). Microbial candidates for the exposure experiments in space include Deinococcus spp.

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An improved method for a suitable derivatization of polyhydroxylated steroids having one or two tert-hydroxyl groups at the 5beta-, 14alpha-, 17alpha-, 24-, and/or 25-positions by capillary gas chromatography (CGC) is described. By using trimethylsilyl triflate as a silylating reagent and 2,6-lutidine as a catalyst, each of 5beta-cholane and 5alpha-cholestane series of steroids was successfully transformed into trimethylsilyl (TMS) ether derivatives to give a single CGC peak under mild conditions. More bulky triethylsilyl (TES) etherification of 14alpha- and 17alpha-hydroxy compounds provided multiple CGC peaks arising from completely- and/or incompletely-derivatized TES ethers accompanied by their thermal elimination products.

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Direct remote functionalization of unactivated carbons by dimethyldioxirane (DMDO) was examined for 3alpha,6- and 3alpha,24-dihydroxy-5beta-cholane derivatives. DMDO oxidation of stereoisomeric methyl 3alpha,6-diacetoxy-5beta-cholanoates caused the direct, unexpected 14alpha- and 17alpha-hydroxylations, in analogy with that of the 5alpha-H analogs, regardless of the differences in stereochemical configuration of the A/B-ring junction and of the acetoxyl groups at C-3 and C-6. On the other hand, the ester derivatives of 3alpha,24-dihydroxy-5beta-cholane with DMDO were transformed into the corresponding 5beta-, 14alpha-, and 17alpha-hydroxy compounds, whereas the ether derivatives yielded the 5beta-hydroxy, 3-oxo, and C-24 oxidized products, accompanied by their dehydrated ones.

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Epimeric 3alpha,7alpha,16- and 3alpha,7alpha,15-trihydroxy-5beta-cholan-24-oic acids and some related compounds were synthesized from chenodeoxycholic acid (CDCA) and ursodeoxycholic acid (UDCA), respectively. The key reaction involved one-step remote oxyfunctionalization of unactivated methine carbons at C-17 of CDCA and at C-14 of UDCA as their methyl ester-peracetate derivatives with dimethyldioxirane (DMDO). After dehydration of the resulting 17alpha- and 14alpha-hydroxy derivatives with POCl(3) or conc.

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