A Facile Mild Deprotection Protocol for 1,3-Dithianes and 1,3-Dithiolanes with 30% Hydrogen Peroxide and Iodine Catalyst in Aqueous Micellar System

Abstract

A simple clean expeditious protocol for the deprotection of 1,3-dithianes and 1,3-dithiolanes has been developed using 30% aqueous hydrogen peroxide activated by iodine catalyst (5 mol%) in water in the presence of sodium dodecyl sulfate (SDS) under essentially neutral conditions. The method showed tolerance for a number of phenol protecting groups such as allyl, benzyl, TBDMS, TBDPS ethers, phenolic acetates, and benzoates as well as amino-protecting BOC, Cbz carbamates without any detectable overoxidation.

Key words

1,3-dithianes - 1,3-dithiolanes - iodine - 30% hydrogen peroxide - sodium dodecyl sulfate (SDS)

References

• 1a Green TW. Wuts PGM. Protective Groups in Organic Synthesis   Wiley; New York: 1999.  3rd ed..
• 1b Kocieneski PJ. Protecting Groups   Thieme; Stuttgart: 1994. 
• 2 Gröbel B.-T. Seebach D. Synthesis  1977,  357 
• 3a Corey EJ. Ericson BW. J. Org. Chem.  1971,  36:  3553 
• 3b Corey EJ. Bock MG. Tetrahedron Lett.  1975,  2643 
• 4a Nishide K. Yokota K. Nakamura D. Sumiya T. Node M. Ueda M. Fuji K. Tetrahedron Lett.  1993,  34:  3425 
• 4b Jones PS. Ley SV. Simkins NS. Whittle AJ. Tetrahedron  1986,  42:  6519 
• 4c Smith RA. Hannah DJ. Synth. Commun.  1979,  9:  301 
• 4d Ho T.-L. Wong CM. Can. J. Chem.  1972,  50:  3740 
• 4e Oksdath-Mansilla G. Peñéñory AB. Tetrahedron Lett.  2007,  48:  6150 
• 4f Haroutounian SA. Synthesis  1995,  39 
• 4g Barton DHR. Cussons NJ. Ley SV. J. Chem. Soc., Chem. Commun.  1977,  751 
• 5 Fetizon M. Jurion M. J. Chem. Soc., Chem. Commun.  1972,  382 
• 6 Schelhass M. Waldman H. Angew. Chem., Int. Ed. Engl.  1996,  35:  2056 
• 7 Stork G. Zhao K. Tetrahedron Lett.  1989,  30:  287 
• 8 Langille NF. Dakin LA. Panek JS. Org. Lett.  2003,  5:  575 
• 9a Wu Y. Shen X. Huang J.-H. Tang C.-J. Liu HH. Hu Q. Tetrahedron Lett.  2002,  43:  6443 
• 9b Nicolaou KC. Mathison CJN. Montagnon T. J. Am. Chem Soc.  2004,  126:  5192 
• 9c Krishnaveni NS. Surendra K. Nageshwar YVD. Rao KR. Synthesis  2003,  2295 
• 9d Corey EJ. Palani A. Tetrahedron Lett.  1995,  36:  7945 
• 9e Meyer SD. Schreiber SL. J. Org. Chem.  1994,  59:  7945 
• 10 Chattopadhyaya JB. Rama Rao AV. Tetrahedron Lett.  1973,  3735 
• 11 Iranpoor N. Firouzabadi H. Shaterian HR. Tetrahedron Lett.  2003,  44:  4769 
• 12a Ceccherelli P. Curini M. Marcrotullio MC. Epifano F. Rosati O. Synlett  1996,  767 
• 12b Desai UV. Pore DM. Tamhankar BV. Jadhav SA. Wadgaonkar PP. Tetrahedron Lett.  2006,  47:  8559 
• 13 Hajipour AR. Mallakpour SE. Bartork IM. Adibi H. Molecules  2002,  7:  674 
• 14 Wakharkar RD. Mahajan VA. Shinde PD. Barhate NB. Tetrahedron Lett.  2002,  43:  6031 
• 15 Kirihara M. Harano A. Tsukiji H. Tajikawa R. Uchiyama T. Hatano A. Tetrahedron Lett.  2005,  46:  6377 
• 16 Handbook of Green Chemistry and Technology   Clark JH. Macquarrie D. Blackwell Science; Oxford: 2002. 
• 17a Jones CW. Applications of Hydrogen Peroxide and Derivatives   Royal Society of Chemistry; Cambridge: 1999. 
• 17b Noyori R. Aoki M. Sato K. Chem. Commun.  2003,  1997 
• 17c Grigoropoulou G. Clark JH. Elings JA. Green Chem.  2003,  5:  1 
• 17d Arends IWCE. Sheldon RA. Top. Catal.  2002,  19:  133 
• 18a Grieco PA. Organic Synthesis in Water   Thomson Science; London: 1998. 
• 18b Li C.-J. Chan T.-H. Organic Reactions in Aqueous Media   Wiley; New York: 1997. 
• 18c Kobayashi S. Manabe K. Acc. Chem. Res.  2002,  35:  209 
• 18d Manabe K. Limura S. Sun X.-M. Kobayashi S. J. Am. Chem. Soc.  2002,  124:  11971 ; and references cited therein
• 19a Ganguly NC. Sukai AK. De S. De P. Synth. Commun.  2001,  31:  1607 
• 19b Ganguly NC. Datta M. Synlett  2004,  659 
• 19c Ganguly NC. Datta M. J. Chem. Res., Synop.  2005,  218 
• 19d Ganguly NC. Barik S. Synthesis  2008,  425 
• 20a Lane BS. Burgess K. Chem. Rev.  2003,  103:  2457 
• 20b Ten Brink G.-J. Arends IWCE. Sheldon RA. Chem. Rev.  2004,  104:  4105 
• 21 Jereb M. Zupan M. Stavber S. Chem. Commun.  2004,  2614 
• 22 Jereb M. Zupan M. Stavber S. Green Chem.  2005,  7:  100 
• 23 Kim MM. Ruck RT. Zhao D. Huffman MA. Tetrahedron Lett.  2008,  49:  4026 
• 24 mitek K. Zupan M. Stavber S. Iskra J. J. Org. Chem.  2007,  72:  6534 
• 25 For regeneration of piperonal from 1 under anhydrous conditions with Fe(NO₃)₃ and montmorilonite K-10 in hexane, see: Hirano M. Ukawa K. Yakabe S. Clark JH. Morimoto T. Synthesis  1997,  858 
• For a review of micellar solubilization and catalysis of organic reactions, see:
• 26a Tascioglu S. Tetrahedron  1996,  52:  11113 ; and references cited therein
• 26b Myers D. Surfactant Science and Technology   VCH; Weinheim: 1992. 
• 26c Dwars T. Paetzold E. Oehme G. Angew. Chem. Int. Ed.  2005,  44:  7174 
• 27 Cerritelli S. Chiarini M. Cerichelli G. Capone M. Marsili M. Eur. J. Org. Chem.  2004,  623 
• 28 Vogel AI. A Textbook of Practical Organic Chemistry   3rd ed.. ELBS and Longman Group Ltd.; London: 1973. 
• 1,3-Dithianes, 1,3-dithiolanes and other thioacetals/ketals were prepared following literature procedures:
• 29a Hatch RP. Shringarpure J. Weinreb SM. J. Org. Chem.  1978,  43:  4172 
• 29b Marshall JA. Belletire JL. Tetrahedron Lett.  1971,  871 
• 30 Chavan SP. Soni PB. Kale RR. Pasupathy K. Synth. Commun.  2003,  33:  879