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2 is not used as the promoting Lewis acid to open epoxide 2 synthetized with Murrays reagent DMDO (for DMDO preparation see: Murray, R.W.; Singh, M. Org. Synth. 1997, 74, 91)
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2 is not used as the promoting Lewis acid to open epoxide 2 synthetized with Murrays reagent DMDO (for DMDO preparation see: Murray, R.W.; Singh, M. Org. Synth. 1997, 74, 91)
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For pioneering studies on ring opening of 1,2-anhydropyranoside (Brigl anhydride) with benzeneselenol, see:;;, and ref 1h
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Santoyo-Gonzáles, F.; Calvo-Flores, F. G.; García-Mendoza, P.; Hernández-Mateo, F.; Isac-García, J.; Robles-Díaz, R. J. Org. Chem. 1993, 58, 6122
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20144370684
-
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references cited therein. Except for 5 and conformationally similar 3,4-di- O- TBDS- or 3,4-di- O -TIPS- d -glucal, other β- phenylselenoglycosides were prepared by the authors in a different way
-
Terauchi, M.; Yahiro, Y.; Abe, H.; Ichikawa, S.; Tovey, S. C.; Dedos, S. G.; Taylor, C. W.; Potter, B. V. L.; Matsuda, A.; Shuto, S. Tetrahedron 2005, 61, 3697 and references cited therein. Except for 5 and conformationally similar 3,4-di- O- TBDS- or 3,4-di- O -TIPS- d -glucal, other β- phenylselenoglycosides were prepared by the authors in a different way
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77953511154
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We found that when using PhSeH as the nucleophile in the direct oxidative glycosylation with glucal 6, Lewis acid is not necessary for coupling to proceed
-
We found that when using PhSeH as the nucleophile in the direct oxidative glycosylation with glucal 6, Lewis acid is not necessary for coupling to proceed.
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35
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0034714332
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Upreti, M.; Ruhela, D.; Vishwakarma, R. A. Tetrahedron 2000, 56, 6577
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0001443980
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For examples of α-approach of electrophilic reagents onto the C(2) position of protected glycals see
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For examples of α-approach of electrophilic reagents onto the C(2) position of protected glycals see: Grewal, G.; Kaila, N.; Franck, R. W. J. Org. Chem. 1992, 57, 2084
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77953515895
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Traces (less than 5%) of the corresponding formate, inseparable from the glycosylation product, are also obtained in the β-phenylselenoglycosylation of glucal 6. Control reaction carried out on β-phenylselenoglycoside 13 and α-phenylselenoglycoside 22, independently synthetized by ring opening of epoxy galactal 21 (see ref 13) with PhSeH, showed the stability of both glycosides to the Gins reaction conditions with no evident isomerization to formate 15. Investigations into the validity of the proposed reaction pathway proposed for the formation of 15 are currently underway
-
Traces (less than 5%) of the corresponding formate, inseparable from the glycosylation product, are also obtained in the β-phenylselenoglycosylation of glucal 6. Control reaction carried out on β-phenylselenoglycoside 13 and α-phenylselenoglycoside 22, independently synthetized by ring opening of epoxy galactal 21 (see ref 13) with PhSeH, showed the stability of both glycosides to the Gins reaction conditions with no evident isomerization to formate 15. Investigations into the validity of the proposed reaction pathway proposed for the formation of 15 are currently underway.
-
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40
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15744397580
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77953482408
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The isomerization from the less carbocationic 24 to the more carbocationic intermediate 25 is favored by the ability of the endocyclic oxygen to stabilize, by conjugative electron-donating effect, the developing of an adjacent carbocationic center
-
The isomerization from the less carbocationic 24 to the more carbocationic intermediate 25 is favored by the ability of the endocyclic oxygen to stabilize, by conjugative electron-donating effect, the developing of an adjacent carbocationic center.
-
-
-
-
43
-
-
0034710476
-
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For examples of cis opening of glycal epoxides metal-catalyzed see
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For examples of cis opening of glycal epoxides metal-catalyzed see: Rainier, J. D.; Cox, J. M. Org. Lett. 2000, 2, 2707
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, pp. 2707
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48
-
-
77953483793
-
-
+ also affords only β-selenoglycoside 13 and β-selenoglycoside 12, respectively
-
+ also affords only β-selenoglycoside 13 and β-selenoglycoside 12, respectively.
-
-
-
-
49
-
-
0032568331
-
-
2 was found to be not able to determine the formation of a fully developed carbocationic species. See refs 9 and 14, as well as the following
-
2 was found to be not able to determine the formation of a fully developed carbocationic species. See refs 9 and 14, as well as the following: Evans, D. A.; Trotter, B. W.; Côté, B. Tetrahedron Lett. 1998, 39, 1709
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, vol.39
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Evans, D.A.1
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-
50
-
-
77953533651
-
-
2 (2 equiv) did not lead to anomeric epimerization after 24 h at 23 °C
-
2 (2 equiv) did not lead to anomeric epimerization after 24 h at 23 °C.
-
-
-
|