Amberlyst-15 as a Heterogeneous Reusable Catalyst for the Synthesis of α-Hydroxy Phosphonates in Water

Abstract

An efficient and simple synthesis of α-hydroxy phos­phonates has been achieved via reaction of aldehydes with tri­methylphosphite in the presence of Amberlyst-15 in water. The reaction is highly selective with excellent yields under mild con­ditions.

Key words

α-hydroxy phosphonates - Abramov reaction - water - Amberlyst-15 - nucleophilic addition

References and Notes

• 1 Cao YJ. Lai YY. Wang X. Li YJ. Xiao WJ. Tetrahedron Lett.  2007,  48:  21 
• 2 Organic Synthesis in Water   Grieco PA. Blackie Academic and Professional; London: 1998. 
• 3 Ranu BC. Banerjee S. Tetrahedron Lett.  2007,  48:  141 
• 4 Hailes HC. Org. Process Res. Dev.  2007,  11:  114 
• See for example:
• 5a Hanaya T. Sugiyama K. Kawamato H. Yamamoto H. Carbohydr. Res.  2003,  338:  1641 
• 5b Rozhko LF. Ragulun W. Russ. J. Gen. Chem.  2005,  75:  533 
• 5c Yamagishi T. Yokomatsu T. Suemune K. Shibuya S. Tetrahedron  1999,  55:  12125 
• 5d Davies SR. Mitchell CP. Cain MC. Devilt PG. Taylor RJ. Kee TP. J. Organomet. Chem.  1998,  550 
• 5e Kralikova A. Budesinky M. Masojidkova M. Rosenberg I. Tetrahedron  2006,  62:  4917 
• 5f El Kam L. Gaultier L. Grimoud L. Dos Santos A. Synlett  2005,  2335 
• 5g Hudson HR. Ismail F. Pianka M. Wan CW. Phosphorus, Sulfur Silicon Relat. Elem.  2000,  164:  245 
• 5h Conant JB. J. Am. Chem. Soc.  1921,  43:  1705 
• 5i Failla S. Finocchiaro P. Consiglio GA. Heteroat. Chem.  2000,  11:  493 
• 5j Dolle RE. Herpin TF. Shimshock YC. Tetrahedron Lett.  2001,  42:  1855 
• 6 Kim DY. Wiemer DF. Tetrahedron Lett.  2003,  44:  2803 
• 7a Neyts J. De Clercq E. Antimicrob. Agents Chemother.  1997,  41:  2754 
• 7b Fleisch H. Endocr. Rev.  1998,  19:  80 
• 7c Snoeck R. Holy A. Dewolf-Peeters C. Van Den Oord J. De Clercq E. Andrei G. Antimicrob. Agents Chemother.  2002,  46:  3356 
• 7d Lee MV. Fong EM. Singer FR. Guenett RS. Cancer Res.  2001,  61:  2602 
• 7e Kafarski P. Lejczak B. J. Mol. Catal. B: Enzym.  2004,  29:  99 
• 7f Patel DV. Rielly-Gauvin K. Ryono DE. Free CA. Rogers WL. Smith SA. DeForrest JM. Oehl RS. Petrillo EW. J. Med. Chem.  1995,  38:  4557 
• 7g Stowasser B. Budt KH. Jian-Qi L. Peyman A. Ruppert D. Tetrahedron Lett.  1992,  33:  6625 
• 7h Zheng X. Nair V. Tetrahedron  1999,  55:  11803 
• 7i Szymanska A. Szymczak M. Boryski J. Stawinski J. Kraszewski A. Collu G. Sanna G. Giliberti G. Loddo R. La Colla P. Bioorg. Med. Chem.  2006,  14:  1924 
• 7j Patel DV. Rielly-Gauvin K. Ryono DE. Tetrahedron Lett.  1990,  31:  5591 
• 8 Fields SC. Tetrahedron  1999,  55:  12237 
• 9 Kaboudin B. Tetrahedron Lett.  2003,  44:  1051 
• 10 Firouzabadi H. Iranpoor N. Sobhani S. Synth. Commun.  2004,  34:  1463 
• 10 Firouzabadi H. Iranpoor N. Sobhani S. Tetrahedron Lett.  2002,  43:  477 
• 10 Kaboudin B. Nazari R. Synth. Commun.  2001,  31:  2245 
• 11 Eymery F. Lorga B. Savignac P. Tetrahedron  1999,  55:  2671 
• 12 Firouzabadi H. Iranpoor N. Sobhani S. Amoozgar Z. Synthesis  2004,  1771 
• 13 Evans DA. Hurst KM. Takacs JM. J. Am. Chem. Soc.  1978,  100:  3467 
• 14 Texier-Boullet F. Foucaud A. Synthesis  1982,  916 
• 15 Texier-Boullet F. Lequitte M. Tetrahedron Lett.  1986,  27:  3515 
• 16 Azizi N. Saidi MR. Phosphorus, Sulfur Silicon Relat. Elem.  2003,  178:  1255 
• 17 Heydari A. Arefi A. Khaksar S. Tajbakhsh M. Catal. Commun.  2006,  7:  98 
• 18 Alexander CW. Albiniak PA. Gibson LR. Phosphorus, Sulfur Silicon Relat. Elem.  2000,  167:  205 
• 19 Saito B. Egami H. Katsuki T. J. Am. Chem. Soc.  2007,  129:  1978 
• 20 Dodda R. Zhao CG. Org. Lett.  2006,  8:  4911 
• 21 Yokomatsu T. Yamagishi T. Shibuya S. Tetrahedron: Asymmetry  1993,  4:  1779 
• 22a Goldeman W. Soroka M. Synthesis  2006,  3019 
• 22b Mizyuk VL. Cherepanova EG. Pudovik MA. Zhurnal Obshchei Khimii  1980,  50:  1878 
• 23 Sum V. Kee TP. J. Chem. Soc., Perkin Trans. 1  1993,  2701 
• 24 Gancarz R. Gancarz I. Walkowiak U. Phosphorus, Sulfur Silicon Relat. Elem.  1995,  104:  45 
• 25 Ko S. Yao C.-F. Tetrahedron Lett.  2006,  47:  8827 
• 26a Tian Q. Zhang S. Yu Q. He M.-B. Yang J.-S. Tetrahedron  2007,  63:  2142 
• 26b Sabou R. Hoelderich WF. Ramprasad D. Weinand R. J. Catal.  2005,  232:  34 
• 26c Yadav JS. Subba Reddy BV. Vishnumurthy P. Tetrahedron Lett.  2005,  46:  1311 
• 26d Honkela ML. Root A. Lindblad M. Krause AOI. Appl. Catal. A  2005,  295:  216 
• 28 He A. Yan B. Thanavaro A. Spilling CD. Rath NP. J. Org. Chem.  2004,  69:  8643 

27

Typical Procedure A solution of benzaldehyde (0.107 g, 1 mmol), trimethyl-phosphite (0.136 g, 1.1 mmol), and Amberlyst-15 (0.1 g) in H₂O (2 mL) was placed in a round-bottomed flask equipped with a magnetic stirrer and was heated at 50 °C. The stirring was continued for 1.5 h. After completion of the reaction as indicated by TLC, the reaction mixture was treated with aq sat. NaHCO₃ solution followed by brine and the product was extracted three times with 5 mL CH₂Cl₂, dried over anhyd MgSO₄, and concentrated to give an oily residue, which was crystallized to give 0.216 g (95%) of dimethyl 1-hydroxy-1-phenylmethylphosphonate.
Spectral Data for Selected ProductsDimethyl 1-Hydroxy-1-phenylmethylphosphonate [19] (Table 1, Entry 1)
IR: 3260 (OH) cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 3.6 (d, J = 10.3 Hz, 3 H), 3.6 (d, J = 10.3 Hz, 3 H), 5.0 (d, 1 H, J = 13.2 Hz), 6.0 (s, OH), 7.3-7.5 (m, 5 H). ¹³C NMR (125 MHz, CDCl₃): δ = 53.7 (d, J _CP = 7.5 Hz), 54.2 (d, J _CP = 7.5 Hz), 69.1 (d, J _CP = 164.0 Hz), 128.8, 129.4, 131.1, 133.8 (d, J _CP = 2.9 Hz).
Dimethyl 1-Hydroxy-1-(4-chlorophenyl)methyl-phosphonate [19] (Table 1, Entry 3)
IR: 3290 (OH) cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 3.6-3.7 (m, 6 H), 5.1 (d, J = 13.4 Hz, 1 H), 6.2 (s, OH), 7.4 (d, J = 8.5 Hz, 2 H), 7.5 (d, J = 8.5 Hz, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 53.7 (d, J _CP = 7.1 Hz), 54.2 (d, J _CP = 7.5 Hz), 69.1 (d, J _CP = 161.1 Hz), 128.8, 129.4, 133.1 (d, J _CP = 3.9 Hz), 138.2.
Dimethyl 1-Hydroxy-3-phenyl-2-propenylphosphonate [28] (Table 1, Entry 4) IR: 3255 (OH) cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 3.8 (d, J _PH = 10.3 Hz, 3 H), 3.8 (d, J _PH = 10.3 Hz, 3 H), 4.7 (s, OH), 6.4 (d, J = 15.9, 6.2 Hz, J _PH = 5.6 Hz, 1 H), 6.8 (d, J = 15.6, 1.5 Hz, J _PH = 4.9 Hz, 1 H), 7.3-7.2 (m, 3 H), 7.4-7.4 (m, 2 H). ¹³C NMR (500 MHz, CDCl₃): δ = 53.7 (d, J _PC = 7.4 Hz), 53.9 (d, J _PC = 7.1 Hz), 69.2 (d, J _PC = 161.0 Hz), 128.4, 127.8, 126.5, 123.5 (d, J _PC = 4.3 Hz), 132.2 (d, J _PC = 13.0 Hz), 136.1 (d, J _PC = 2.9 Hz).
Dimethyl 1-Hydroxybutylphosphonate [17] (Table 1, Entry 11)
IR: 3312 (OH) cm^-1. ¹H NMR (90 MHz, CDCl₃): δ = 1.0 (t, 3 H), 1.8-1.1 (m, 4 H), 2.7 (m, 1 H), 3.7 (d, ³ J _PH = 5.4 Hz, 3 H), 3.8 (d, ³ J _PH = 5.4 Hz, 3 H), 3.9 (s, OH). ¹³C NMR (22.5 MHz, CDCl₃): δ = 13.8 (d, ⁴ J _PC = 19.1 Hz, CH₃), 19.9 (d, ³ J _PC = 11.8 Hz, CH₂), 29.0 (d, ² J _PC = 7.4 Hz, CH₂), 51.1 (d, ² J _PC = 7.3 Hz, OCH₃), 52.2 (d, ² J _PC = 7.3 Hz, OCH₃), 56.8 (d, ¹ J _PC = 136.8 Hz, OCH₃).
Dimethyl 1-Hydroxy-2-methylpropylphosphonate [17] (Table 1, Entry 13) IR: 3313 (OH) cm^-1. ¹H NMR (90 MHz, CDCl₃): δ = 0.8 (m, 3 H), 1.9 (m, 1 H), 3.6 (m, 1 H), 3.6 (d, ³ J _PH = 4.4 Hz, 3 H), 3.7 (d, ³ J _PH = 4.4 Hz, 3 H), 4.8 (s, O H). ¹³C NMR (22.5 MHz, CDCl₃): δ = 17.4 (d, ⁴ J _PC = 7.0 Hz, CH₃), 19.4 (d, ³ J _PC = 9.5 Hz, CH₂), 29.9 (d, ² J _PC = 8.0, CH), 52.4 (² J _PC = 6.5 Hz, OCH₃), 52.6 (² J _PC = 6.5 Hz, OCH₃), 73.2 (¹ J _PC = 148.4 Hz, CH).
Dimethyl 1-Hydroxy-1-furylmethylphosphonate [17] (Table 1, Entry 14)
¹H NMR (90 MHz, CDCl₃): δ = 1.3 (s, OH), 3.7 (d, ³ J _PH = 5.8 Hz, 3 H), 3.9 (d, ³ J _PH = 5.8 Hz, 3 H), 5.0 (d, ² J _PH = 13.5 Hz, 1 H), 6.4-6.6 (m, 2 H), 7.4 (s, 1 H). ¹³C NMR (22.5 MHz, CDCl₃): δ = 53.6 (d, ² J _PC = 2.7 Hz, OCH₃), 53.9 (d, ² J _PC = 2.7 Hz, OCH₃), 64.2 (d, ¹ J _PC = 167.8 Hz, CH), 109.3 (d, ³ J _PC = 6.4 Hz, C), 110.7 (s, CH), 142.8 (d, ³ J _PC = 1.8 Hz, CH), 149.9 (s, CH).