Highly Efficient Discrimination of Fluorous Tags by β-Cyclodextrin Columns: New Isolation Method for Fluorous Mixture Synthesis

Abstract

High performance liquid chromatography (HPLC) packed with β-cyclodextrin columns eluted by reversed phase or fluorous phase shows excellent discrimination of fluorous tags. β-Cyclodextrin columns are superior to fluorous silica gel columns in view of efficient separation of compounds bearing short (CF₃) to long (C₉F₁₉) tag.

β-cyclodextrin - chromatography - separation technique - combinatorial chemistry - fluorine chemistry

References

1 Nishikido J. Nanbo M. Yoshida A. Nakajima H. Matsumoto Y. Mikami K. Synlett  2002,  1613 

2 Wilson LD. Verrall RE. J. Phys. Chem. B  1997,  101:  9270 

3a Curran DP. Furukawa T. Org. Lett.  2002,  4:  2233 

3b Zhang Q. Rivkin A. Curran DP. J. Am. Chem. Soc.  2002,  124:  5774 

3c Curran DP. Oderaotoshi Y. Tetrahedron  2001,  57:  5234 

3d Luo Z. Zhang Q. Oderaotoshi Y. Curran DP. Science  2001,  291:  1766 

4 Curran DP. Synlett  2001,  1488 

5a Kamiusuki T. Monde T. Yano K. Yoko T. Konakahara T. Chromatographia  1999,  49:  649 

5b Konakahara T. Okada S. Monde T. Nakayama N. Furuhashi J. Sugaya J. Nihon Kagaku Kaishi  1991,  12:  1638 

5c Konakahara T, Nakayama N, and Monde T. inventors; Jpn. Pat. Dec.  2505267. 

6

SUMICHIRAL OA-7000 series are sold by Sumika Chemical Analysis Service. Catalog about SUMICHIRAL OA-7000 series: Welcome to SUMICHIRAL OA third edition. URL: http://www.scas.co.jp/.

7

SUMICHIRAL OA-7000 is the column with unmodified β-CD bonded to the silica gel via saccharide (glucuroyl gluconoyl group) spacer; SUMICHIRAL OA-7100 is the column with unmodified β-CD bonded to the silica gel via alkyl group spacer; SUMICHIRAL OA-7500 is the column with β-CD, in which hydroxyl group is protected by methyl group, bonded to the silica gel via alkyl group spacer.

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Fluorinated sulfonamides (PhSO₂NHCH₂C_nF_n+1, n = 1, 3, 7) were also separated with OA-7000 or OA-7100 (mobile phase: gradient of MeOH/H₂O).

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Retention time of esters 1a-c was as follows; 1a: 19.1 min, 1b: 28.6 min, 1c: 39.2 min.

10

Retention time of sulfonates 2a-e with OA-7100 was as follows; 2a: 23.1 min, 2b: 16.9 min, 2c: 14.3 min, 2d: 10.8 min, 2e: 10.2 min.

OD-H is packed with the cellulose 3,5-dimethylphenylcarbamate and helical structure is proposed for cellulose tris(phenylcarbamate). Review:

11a Nakano T. Okamoto Y. Chem. Rev.  2001,  101:  4013 

11b Yashima E. Yamamoto C. Okamoto Y. Synlett  1998,  344 

11c Yashima E. Okamoto Y. Bull. Chem. Soc. Jpn.  1995,  68:  3289 

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ZEORORA-H is 1,1,2,2,3,3,4-heptafluorocyclopentane and sold by ZEON CORPORATION. URL of ZEON CORPORATION: http://www.zeon.co.jp/.