Conversion of Alcohols to Thiols via Tosylate Intermediates

Abstract

High yielding syntheses of mercapto terminated monodisperse dimer, trimer, and tetramer ethyleneoxide oligomers and of p-hydroxyphenethyl thiol via an alcohol-tosylate-thiol route are reported. Comparisons are made with the more conventional alcohol-bromide-thiol route.

thiols - esters - alcohols - thiourea - ethyleneglycol oligomer

References

1 Ulman A. Chem. Rev.  1996,  96:  1533 

2 Hostetler MJ. Murray RW. Curr. Opin. Colloid Interface Sci.  1997,  2:  42 

3 Shipway AN. Katz E. Wilner I. ChemPhysChem  2000,  1:  18 

4 Silin V. Weetall H. Vanderah DJ. J. Colloid Interface Sci.  1997,  185:  94 

5 Wohtjen H. Snow AW. Anal. Chem.  1998,  70:  2856 

6 Foos EE. Snow AW. Twigg ME. Ancona MG. Chem. Mater.  2002,  14:  2401 

7 Urquhart GG. Gates JW. Connor R. Org. Synth., Coll. Vol. III   John Wiley and Sons; London: 1955.  p.363 

8 Kocienski PJ. Cerniglaro G. Feldstein G. J. Org. Chem.  1977,  42:  353 

9 Wolff JJ. Frenking G. Harms K. Chem. Ber.  1991,  124:  551 

10a Wardell JL. In The Chemistry of the Thiol Group   Patai S. John Wiley & Sons; New York: 1974.  Part 1. p.163 

10b Sandler SR. Karo W. In Organic Functional Group Preparations   Academic Press; New York: 1983.  p.585 

10c Wagner RB. Zook HD. In Synthetic Organic Chemistry   John Wiley & Sons; New York: 1953.  p.778 

11 Houk J. Whitesides GM. J. Am. Chem. Soc.  1987,  109:  6825 

12 Goor G. Antennis M. Phosphorus Sulfur  1976,  1:  81 

13 Martin DJ. Greco CC. J. Org. Chem.  1968,  33:  1275 

14 Bartz M. Kuther J. Nelles G. Weber N. Seshadri R. Tremel W. J. Mater. Chem.  1999,  9:  1121 

15 While this manuscript was under review, a similar synthesis involving conversion of a hydroxyl terminated poly(ethylene glycol) to the thiol terminated analog via thioacetate displacement of a tosylate intermediate was reported: Lee D. Donkers RL. DeSimone JM. Murray RW. J. Am. Chem. Soc.  2003,  125:  1182