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

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

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.