Facile and Efficient Oxidative Transformation of Primary Alcohols to Methyl Esters in Water Using Hypervalent Iodine(III) Reagents

Abstract

A facile and direct oxidative esterification of primary alcohols in water using a combination of the hypervalent iodine(III) reagent, iodosobenzene (PhIO), and KBr has been developed. This methodology is expected to be environmentally benign since it uses a recyclable polymer-supported iodine(III) reagent in water.

Key words

alcohols - oxidations - esterification - hypervalent iodine - polymers

References

• 1a Protective Group in Organic Synthesis   3rd ed.:  Greene TM. Wutz PG. Wiley; New York: 1999.  p.149 
• 1b Protective Group in Organic Synthesis   3rd ed.:  Greene TM. Wutz PG. Wiley; New York: 1999.  p.373 
• 2a Larock RC. Comprehensive Organic Transformation   2nd ed.:  VCH; New York: 1999.  p.1656 
• 2b March J. Advanced Organic Chemistry   John Wiley & Sons; New York: 1992.  p.1196 
• 3a Kaneko R. Seki K. Suzuki M. Chem. Ind. (London)  1971,  1016 
• 3b Smith AB. Sulikowski GA. Sulikowski MM. Fujimoto K. J. Am. Chem. Soc.  1992,  114:  2567 
• 3c Foot JS. Kanno H. Giblin GMP. Taylor RJK. Synlett  2002,  1293 
• 4a Corey EJ. Samuelsson B. J. Org. Chem.  1984,  49:  4735 
• 4b Guest AW. Tetrahedron Lett.  1986,  27:  3049 
• 5 Milovanovic JN. Vasojevic M. Gojkovic S. J. Chem. Soc., Perkin Trans. 2  1991,  1231 
• 6 McDonald CE. Holcomb HL. Leathers TW. Kennedy KE. Microchem. J.  1993,  47:  115 
• 7 McDonald CE. Nice LE. Shaw AW. Nestor NB. Tetrahedron Lett.  1993,  34:  2741 
• Recent reviews see:
• 8a Stang PJ. Zhdankin VV. Chem. Rev.  1996,  96:  1123 
• 8b Kita Y. Takada T. Tohma H. Pure & Appl. Chem.  1996,  68:  627 
• 8c Varvoglis A. Hypervalent Iodine in Organic Synthesis   Academic Press; San Diego: 1997. 
• 8d Kitamura T. Fujiwara Y. Org. Prep. Proced. Int.  1997,  29:  409 
• 8e Ochiai M. In Chemistry in Hypervalent Compounds   Akiba K. Wiley-VCH; New York: 1999.  Chap. 12.
• 8f Wirth T. Hirt UH. Synthesis  1999,  1271 
• 8g Zhdankin VV. Stang PJ. Chem. Rev.  2002,  102:  2523 
• 8h Hypervalent Iodine Chemistry (Top. Curr. Chem. 224)   Wirth T. Springer-Verlag; Berlin, Heidelberg: 2003. 
• 9a Tohma H. Takizawa S. Maegawa T. Kita Y. Angew. Chem. Int. Ed.  2000,  39:  1306 
• 9b Tohma H. Maegawa T. Takizawa S. Kita Y. Adv. Synth. Catal.  2002,  344:  328 
• Reviews see:
• 11a Drewry DH. Coe DM. Poon S. Med. Res. Rev.  1999,  19:  97 
• 11b Ley SV. Baxendale IR. Bream RN. Jackson PS. Leach AG. Longbottom DA. Nesi M. Scott JS. Storer RI. Taylor SJ. J. Chem. Soc., Perkin Trans. 1  2000,  3815 
• 11c Bhalay G. Dunstan A. Glen A. Synlett  2000,  1846 
• 11d Kirschning A. Monenschein H. Wittenberg R. Angew. Chem. Int. Ed.  2001,  40:  650 
• 11e Togo H. Sakuratani K. Synlett  2002,  1966 
• 12a Togo H. Nogami G. Yokoyama M. Synlett  1998,  534 
• 12b Togo H. Abe S. Nogami G. Yokoyama M. Bull. Chem. Soc. Jpn.  1999,  72:  2351 
• 12c Abe S. Sakuratani K. Togo H. Synlett  2001,  22 
• 12d Abe S. Sakuratani K. Togo H. J. Org. Chem.  2001,  66:  6174 
• 13a Ley SV. Thomas AW. Finch H. J. Chem. Soc., Perkin Trans 1  1999,  669 
• 13b Ley SV. Schucht O. Thomas AW. Murray PJ. J. Chem. Soc., Perkin Trans. 1  1999,  1251 
• 13c Baxendale IR. Ley SV. Piutti C. Angew. Chem. Int. Ed.  2002,  41:  2194 
• 13d Baxendale IR. Lee A.-L. Ley SV. J. Chem. Soc., Perkin Trans. 1  2002,  1850 
• 14a Tohma H. Morioka H. Takizawa S. Arisawa M. Kita Y. Tetrahedron  2001,  57:  345 
• 14b Tohma H. Morioka H. Harayama Y. Hashizume M. Kita Y. Tetrahedron Lett.  2001,  42:  6899 
• 15a Okawara M. Mizuta K. Kogyo Kagaku Zasshi  1961,  64:  232 
• 15b Yamada Y. Okawara M. Makromol. Chem.  1972,  152:  153 
• 15c Hallensleben ML. Angew. Makromol. Chem.  1972,  27:  223 

10

Among the typical hypervalent iodine(III or V) reagents, PhIO gave the best yield [75% yield], while other reagents such as phenyliodine diacetate (PIDA) [47% yield], phenyliodine bis(trifluoroacetate) (PIFA) [40% yield], Dess-Martin periodinane [trace], and o-iodoxybenzoic acid [trace], were also examined under the reaction conditions described in Table [1] .

16

General Experimental Procedure: Oxidation with PhIO-KBr: To a stirred solution of 1 (1.0 mmol) and KBr (0.5 mmol) in MeOH (1 mL) was added dropwise 0.5 N HCl aq (0.5 mL). PhIO (3.5 mmol) was added to the vigorously stirred solution and stirring was continued for several hours at room temperature while checking the reaction progress by GC or TLC. After completion of the reaction, water (ca. 1.5 mL) was added to the mixture. The mixture was filtrated through BOND ELUT C 18 (Varian), washed with a small amount of water, and extracted with Et₂O. The filtrate was dried with MgSO₄, and evaporated. The residue was purified by column chromatography (SiO₂/n-hexane-Et₂O) to give pure 2. Oxidation with PDAIS-KBr: To a stirred solution of 1 (1.0 mmol) and KBr (1.0 mmol) in MeOH (2 mL) was added dropwise 0.5 N HCl aq (1 mL). PDAIS (prepared by the reported procedure [9b] ) (3.0 mmol) was added to the vigorously stirred solution and stirring was continued for several hours at room temperature. After completion of the reaction, water (ca. 3 mL) was added to the mixture. The mixture was filtered through BOND ELUT C 18 (Varian) and washed with a small amount of water to remove KBr. The residue was extracted with Et₂O, and the filtrate was dried and evaporated. The residue was purified by column chromatography to give pure 2.