Download PDF
Synlett 2011(11): 1613-1617  
DOI: 10.1055/s-0030-1260788
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Preparation and Reactivity of Polystyrene-Supported Iodosylbenzene: Convenient Recyclable Oxidizing Reagent and Catalyst

Jiang-Min Chen*a,b, Xiao-Mei Zengb, Kyle Middletonb, Mekhman S. Yusubovc, Viktor V. Zhdankin*b
a College of Biological and Chemical Engineering, Jiaxing University, 56 South Yuexiu Rd, Jiaxing 314001, P. R. of China
e-Mail: chemcjm@yahoo.com.cn;
b Department of Chemistry and Biochemistry, University of Minnesota Duluth, 1039 University Dr., Duluth, MN 55812, USA
Fax: +1(218)7267394; e-Mail: vzhdanki@d.umn.edu;
c The Siberian State Medical University and The Tomsk Polytechnic University, 634050 Tomsk, Russia
Further Information

Publication History

Received 23 March 2011
Publication Date:
15 June 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

A facile preparation of novel polystyrene-supported iodosylbenzene (PS-ISB, loading of IO up to 1.50 mmol/g) from iodopolystyrene is described. This resin has been successfully used for efficient oxidation of a diverse collection of alcohols to aldehydes and ketones in the presence of BF3˙OEt2. PS-ISB can also be employed as efficient co-catalyst in combination with RuCl3 in the catalytic oxidation of alcohols and aromatic hydrocarbons, respectively, to corresponding carboxylic acids and ketones using Oxone as the stoichiometric oxidant.

Key words

polymers - iodine - oxidation - iodosylbenzene - recyclable reagent

    References and Notes

  • 1a Varvoglis A. Hypervalent Iodine in Organic Synthesis   Academic Press; London: 1997. 
    Google Scholar
  • 1b Hypervalent Iodine Chemistry   Wirth T. Springer; Berlin: 2003. 
    Google Scholar
  • 1c Koser GF. Aldrichimica Acta  2001,  34:  89 
    Google Scholar
  • 1d Koser GF. Adv. Heterocycl. Chem.  2004,  86:  225 
    Google Scholar
  • 1e Moriarty RM. J. Org. Chem.  2005,  70:  2893 
    Google Scholar
  • 1f Zhdankin VV. Stang PJ. Chem. Rev.  2008,  108:  5299 
    Google Scholar
  • 1g Ladziata U. Zhdankin VV. ARKIVOC  2006,  (ix):  26 
    Google Scholar
  • 1h Ciufolini MA. Braun NA. Canesi S. Ousmer M. Chang J. Chai D. Synthesis  2007,  3759 
    Google Scholar
  • 1i Zhdankin VV. Science of Synthesis   Vol. 31a:  Thieme; Stuttgart: 2007.  Chap. 31.4.1. p.161 
    Google Scholar
  • 1j Ochiai M. Miyamoto K. Eur. J. Org. Chem.  2008,  4229 
    Google Scholar
  • 1k Dohi T. Kita Y. Chem. Commun.  2009,  2073 
    Google Scholar
  • 1l Ladziata U. Zhdankin VV. Synlett  2007,  527 
    Google Scholar
  • 1m Quideau S. Pouysegu L. Deffieux D. Synlett  2008,  467 
    Google Scholar
  • 1n Yusubov MS. Zhdankin VV. Mendeleev Commun.  2010,  20:  185 
    Google Scholar
  • 1o Zhdankin VV. ARKIVOC  2009,  (i):  1 
    Google Scholar
  • 1p Uyanik M. Ishihara K. Chem. Commun.  2009,  2086 
    Google Scholar
  • 1q Ngatimin M. Lupton DW. Aust. J. Chem.  2010,  63:  653 
    Google Scholar
  • 1r Yusubov MS. Nemykin VN. Zhdankin VV. Tetrahedron  2010,  66:  5745 
    Google Scholar
  • 1s Satam V. Harad A. Rajule R. Pati H. Tetrahedron  2010,  66:  7659 
    Google Scholar
  • 1t Uyanik M. Ishihara K. Aldrichimica Acta  2010,  43:  83 
    Google Scholar
  • 1u Merritt EA. Olofsson B. Synthesis  2011,  517 
    Google Scholar
  • 1v Brand JP. Gonzalez DF. Nicolai S. Waser J. Chem. Commun.  2011,  47:  102 
    Google Scholar
  • 1w Zhdankin VV. J. Org. Chem.  2011,  76:  1185 
    Google Scholar
  • 2a Groves JT. Nemo TE. Myers RS. J. Am. Chem. Soc.  1979,  101:  1032 
    Google Scholar
  • 2b Cytochrome P450: Structure, Mechanism, and Biochemistry   Ortiz de Montellano PR. Kluwer Academic/Plenum Publishers; New York: 2005. 
    Google Scholar
  • 2c Metalloporphyrins in Catalytic Oxidations   Sheldon RA. Marcel Dekker; New York: 1994. 
    Google Scholar
  • 2d Rose E. Andrioletti B. Zrig S. Quelquejeu-Etheve M. Chem. Soc. Rev.  2005,  34:  573 
    Google Scholar
  • 2e Simonneaux G. Tagliatesta P. J. Porphyrins Phthalocyanines  2004,  8:  1166 
    Google Scholar
  • 2f Bernadou J. Meunier B. Adv. Synth. Catal.  2004,  346:  171 
    Google Scholar
  • 2g Vinhado FS. Martins PR. Iamamoto Y. Curr. Top. Catal.  2002,  3:  199 
    Google Scholar
  • 2h Meunier B. Robert A. Pratviel G. Bernadou J. The Porphyrin Handbook   Vol. 4:  Academic Press; San Diego: 2000.  p.119 
    Google Scholar
  • 2i Groves JT. Shalyaev K. Lee J. The Porphyrin Handbook   Vol. 4:  Academic Press; San Diego: 2000.  p.17 
    Google Scholar
  • 2j Moro-oka Y. Akita M. Catal. Today  1998,  41:  327 
    Google Scholar
  • 2k Noyori R. Asymmetric Catalysis in Organic Synthesis   Wiley; New York: 1994. 
    Google Scholar
  • 3a Moriarty RM. Kosmeder JW. Zhdankin VV. In Encyclopedia of Reagents for Organic Synthesis   Paquette LA. Wiley; Chichester: 2004. 
    Google Scholar
  • 3b Koposov AY. Netzel BC. Yusubov MS. Nemykin VN. Nazarenko AY. Zhdankin VV. Eur. J. Org. Chem.  2007,  4475 
    Google Scholar
  • 3c Nemykin VN. Koposov AY. Netzel BC. Yusubov MS. Zhdankin VV. Inorg. Chem.  2009,  48:  4908 
    Google Scholar
  • 4 An explosion of iodosylbenzene upon drying at elevated temperature in vacuum has recently been reported: McQuaid KM. Pettus TRR. Synlett  2004,  2403 
    Article in Thieme ConnectGoogle Scholar
  • 5 Togo H. Sakuratani K. Synlett  2002,  1966 
    Article in Thieme ConnectGoogle Scholar
  • 6a Chen JM. Huang X. Synthesis  2004,  2459 
    Google Scholar
  • 6b Chen JM. Huang X. Synthesis  2004,  1577 
    Google Scholar
  • 6c Chen JM. Wu LL. Huang X. Chin. Chem. Lett.  2004,  15:  1387 
    Google Scholar
  • 6d Chen J.-M. Zeng X.-M. Zhdankin VV. Synlett  2010,  2771 
    Google Scholar
  • 6e Chen J.-M. Zeng X.-M. Middleton K. Zhdankin VV. Tetrahedron Lett.  2011,  52:  1952 
    Google Scholar
  • 6f Chen JM. Huang X. Synlett  2004,  552 
    Google Scholar
  • 7a Togo H. Nogami G. Yokoyama M. Synlett  1998,  534 
    Google Scholar
  • 7b Togo H. Abe S. Nogami G. Yokoyama M. Bull. Chem. Soc. Jpn.  1999,  72:  2351 
    Google Scholar
  • 9a Yusubov MS. Wirth T. Org. Lett.  2005,  7:  519 
    Google Scholar
  • 9b Koposov AY. Netzel BC. Yusubov MS. Nemykin VN. Nazarenko AY. Zhdankin VV. Eur. J. Org. Chem.  2007,  4475 
    Google Scholar
  • 11 Geraskin IM. Pavlova O. Neu HM. Yusubov MS. Nemykin VN. Zhdankin VV. Adv. Synth. Catal.  2009,  351:  733 
    CrossrefGoogle Scholar
  • 12 Yusubov MS. Zagulyaeva AA. Zhdankin VV. Chem. Eur. J.  2009,  15:  11091 
    CrossrefGoogle Scholar
8

Preparation of PS-ISB (2) PS-DIB (1,7 1.430 g, 3.0 mmol) and NaOH (0.400 g, 10.0 mmol) were grinded intensively in a mortar at r.t. for 10 min. The resulting mixture was left to stay at r.t. for 2 h, then H2O (15 mL) was added and stirred overnight, the mixture was filtered, washed with H2O (3 × 3 mL), acetone (3 × 3 mL), and Et2O (3 × 3 mL) subsequently, and then dried in vacuum to give a yellow powder (1.05 g). Elem. Anal. (%): O, 8.68; I, 37.19. IR (KBr): ν = 761 (I=O) cm-¹.

10

General Procedure for Oxidations Using PS-ISB (2)
To a vigorously stirred suspension of PS-ISB (2, 0.3 mmol) in CH2Cl2 (2 mL), BF3˙OEt2 (0.040 mL) was added, and the resulting mixture was stirred at r.t. for 15 min. To the mixture, the appropriate alcohol (0.2 mmol) or Ph3P (0.2 mmol) or anthracene (0.1 mmol) was added. The resulting mixture was stirred at r.t. for the indicated time (Table  [¹] ). A portion of the crude reaction mixture (100 µL) was poured into a flask with Et2O (0.5 mL) to precipitate PS-IB, then the mixture was passed through a 2-3 cm of silica gel suspended in a Pasteur pipette, and the resulting solution was analyzed by GC-MS to determine the conversion of organic substrates.

13

Typical Procedure of the PS-ISB/RuCl 3 -Cocatalyzed Oxidation of Alcohols Oxone (0.92 g, 1.5 mmol) was added to a mixture of 1-phenylethanol (122 mg, 1 mmol, Table  [²] , entry 7), PS-ISB (2, 0.070 g, 0.1 mmol, 10 mol%), and RuCl3 (10 µL of 0.20 M solution in H2O, 0.002 mmol, 0.2 mol%) in MeCN (3 mL) and H2O (3 mL) in one portions under stirring at r.t. (the reaction was monitored by TLC by the disappearance of 1-phenylethanol). Then EtOAc (15 mL) and H2O (20 mL) were added, and the mixture was stirred for 5 min. The polymeric catalyst (PS-ISB) was filtered, washed with H2O (2 × 2 mL) and EtOAc (2 × 2 mL), and collected for next run. The organic solution was separated, and the aqueous phase and extracted with EtOAc (2 × 15 mL). The organic solutions were combined, washed with NaCl (sat. solution, 20 mL), and dried over anhyd Na2SO4. Removal of the solvent under vacuum afforded acetophenone (114 mg, 95%). The oxidation of other alcohols and hydrocarbons (Table  [²] ) was performed by using a similar procedure.