An Efficient Method for Phosphorylation of Alcohols: Preparation of Por­phyrin-Derived Phosphates

Abstract

An effective method for the phosphorylation of phenols and various alcohols including porphyrins bearing hydroxyl groups was developed. The reaction of 6,7-bis(3-hydroxypropyl)-1,3,5,8-tetramethyl-2,4-divinylporphyrin with dialkyl chlorophosphate in the presence of DABCO as both a catalyst and a proton scavenger gave the desired phosphate in 97% yield.

Key words

phosphorylation - dialkyl chlorophosphate - porphyrin - protoporphyrin IX

• References and Notes

• 1 Quin LD In A Guide to Organophosphorus Chemistry . Wiley-Interscience; New York: 2000: 351-357
• 2 Tebby JC, Allen DW, Loakes D, Pajkert R. Organophoshorus Chemistry . Vol. 39 RSC; Cambridge: 2010
• 3 Westheimer FH. Science 1987; 235: 1173
• 4 Hecker SJ, Erion MD. J. Med. Chem. 2008; 51: 2328
• 5 Rautio J, Kumpulainen H, Heimbach T, Oliyai R, Oh D, Järvinen T, Savolainen J. Nat. Rev. Drug. Discov. 2008; 7: 255
• 6 Slotin LA. Synthesis 1977; 737
• 7 Perich JW, Johns RB. Tetrahedron Lett. 1987; 28: 101
• 8 Stowell JK, Widlanski TS. Tetrahedron Lett. 1995; 36: 1825
• 9 Oza VB, Corcoran RC. J. Org. Chem. 1995; 60: 3680
• 10 Ireland RE, Muchmore DC, Hengartner U. J. Am. Chem. Soc. 1972; 94: 5098
• 11 Granata A, Perlin AS. Carbohydr. Res. 1981; 94: 165
• 12 Mora N, Lacombe JM, Pavia AA. Tetrahedron Lett. 1993; 34: 2461
• 13 Salzmann TN, Ratcliffe RW, Christensen BG, Bouffard FA. J. Am. Chem. Soc. 1980; 102: 6161
• 14 Sabesan S, Neira S. Carbohydr. Res. 1992; 223: 169
• 15 Sculimbrene BR, Miller SJ. J. Am. Chem. Soc. 2001; 123: 10125
• 16 Jones S, Selitsianos D. Org. Lett. 2002; 4: 3671
• 17 Jones S, Selitsianos D, Thompson KJ, Toms S. J. Org. Chem. 2003; 68: 5211
• 18 Jones S, Smanmoo C. Org. Lett. 2005; 7: 3271
• 19 Kadish KM, Smith KM, Guilard R. Phototheraphy, Radioimmunotheraphy and Imaging In Handbook of Porphyrin Science . Vol. 4. Academic Press; San Diego: 2000
• 20 Matsushita Y, Hasegawa E, Eshima K, Tsuchida E. Chem. Lett. 1983; 1387
• 21 Komatsu T, Yamada K, Yanagisawa S, Nishide H, Tsuchida E. Chem. Lett. 1994; 1953
• 22 Berlin K, Jain RK, Simon MD, Richert C. J. Org. Chem. 1998; 63: 1527
• 23a Ganesan K, Kovtun A, Neumann S, Heumann R, Epple M. J. Mater. Chem. 2008; 18: 3655
• 23b Bonar-Law RP. J. Org. Chem. 1996; 61: 3623
• 24 Sargsyan G, MacLeod BL, Tohgha U, Balaz M. Tetrahedron 2012; 68: 2093
• 25 Liang G, Wang L, Yang Z, Koon H, Mak N, Chang CK, Xu B. Chem. Commun. 2006; 5021
• 26 Borbas KE, Mroz P, Hamblin MR, Lindsey JS. Bioconjugate Chem. 2006; 17: 638
• 27 Yao Z, Borbas KE, Lindsey JS. New J. Chem. 2008; 32: 436
• 28 Sylvain I, Zerrouki R, Granet R, Huang YM, Lagorce JF, Guilloton M, Blais JC, Krausz P. Bioorg. Med. Chem. 2002; 10: 57
• 29 Smith KM, Eivazi F, Martynenko Z. J. Org. Chem. 1981; 46: 2189
• 30 Bordwell pK _a Table (Acidity in DMSO). Available online: http://www.chem.wisc.edu/areas/reich/pkatable/.
• 31 Zwierzak A. Synthesis 1976; 305
• 32 Szajnman SH, Linares GG, Moro P, Rodriguez JB. Eur. J. Org. Chem. 2005; 3687
• 33 Bartlett PD, Lonzetta CM. J. Am. Chem. Soc. 1983; 105: 1984
• 34 Badet B, Julia M, Rolando C. Synthesis 1982; 291
• 35 Bracha P, O’Brien RD. Biochemistry 1968; 7: 1545