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

Mahmood Tajbakhsh; Akbar Heydari; Mohammad A. Khalilzadeh; Moslem M. Lakouraj; Behi Zamenian; Samad Khaksar

doi:10.1055/s-2007-985595

LETTER

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

Mahmood Tajbakhsh*^a, Akbar Heydari^b, Mohammad A. Khalilzadeh^c, Moslem M. Lakouraj^a, Behi Zamenian^a, Samad Khaksar^b
^a Department of Chemistry, Faculty of Basic Science, Mazandaran University, Babolsar 47415, Iran
Fax: +98(11252)42002; e-Mail: tajbaksh@umz.ac.ir;
^b Department of Chemistry, Tarbiat Modares University, P. O. Box 14155-4838, Tehran 18716, Iran
^c Department of Chemistry, Islamic Azad University, P. O. Box 163, Qaemshahr, Iran

Abstract

All articles of this category

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

Full Text

References

References and Notes

<A NAME="RD15807ST-1">1</A> Cao YJ. Lai YY. Wang X. Li YJ. Xiao WJ. Tetrahedron Lett. 2007, 48: 21

<A NAME="RD15807ST-2">2</A> Organic Synthesis in Water Grieco PA. Blackie Academic and Professional; London: 1998.

<A NAME="RD15807ST-3">3</A> Ranu BC. Banerjee S. Tetrahedron Lett. 2007, 48: 141

<A NAME="RD15807ST-4">4</A> Hailes HC. Org. Process Res. Dev. 2007, 11: 114

See for example:

<A NAME="RD15807ST-5A">5a</A> Hanaya T. Sugiyama K. Kawamato H. Yamamoto H. Carbohydr. Res. 2003, 338: 1641

<A NAME="RD15807ST-5B">5b</A> Rozhko LF. Ragulun W. Russ. J. Gen. Chem. 2005, 75: 533

<A NAME="RD15807ST-5C">5c</A> Yamagishi T. Yokomatsu T. Suemune K. Shibuya S. Tetrahedron 1999, 55: 12125

<A NAME="RD15807ST-5D">5d</A> Davies SR. Mitchell CP. Cain MC. Devilt PG. Taylor RJ. Kee TP. J. Organomet. Chem. 1998, 550

<A NAME="RD15807ST-5E">5e</A> Kralikova A. Budesinky M. Masojidkova M. Rosenberg I. Tetrahedron 2006, 62: 4917

<A NAME="RD15807ST-5F">5f</A> El Ka m L. Gaultier L. Grimoud L. Dos Santos A. Synlett 2005, 2335

<A NAME="RD15807ST-5G">5g</A> Hudson HR. Ismail F. Pianka M. Wan CW. Phosphorus, Sulfur Silicon Relat. Elem. 2000, 164: 245

<A NAME="RD15807ST-5H">5h</A> Conant JB. J. Am. Chem. Soc. 1921, 43: 1705

<A NAME="RD15807ST-5I">5i</A> Failla S. Finocchiaro P. Consiglio GA. Heteroat. Chem. 2000, 11: 493

<A NAME="RD15807ST-5J">5j</A> Dolle RE. Herpin TF. Shimshock YC. Tetrahedron Lett. 2001, 42: 1855

<A NAME="RD15807ST-6">6</A> Kim DY. Wiemer DF. Tetrahedron Lett. 2003, 44: 2803

<A NAME="RD15807ST-7A">7a</A> Neyts J. De Clercq E. Antimicrob. Agents Chemother. 1997, 41: 2754

<A NAME="RD15807ST-7B">7b</A> Fleisch H. Endocr. Rev. 1998, 19: 80

<A NAME="RD15807ST-7C">7c</A> Snoeck R. Holy A. Dewolf-Peeters C. Van Den Oord J. De Clercq E. Andrei G. Antimicrob. Agents Chemother. 2002, 46: 3356

<A NAME="RD15807ST-7D">7d</A> Lee MV. Fong EM. Singer FR. Guenett RS. Cancer Res. 2001, 61: 2602

<A NAME="RD15807ST-7E">7e</A> Kafarski P. Lejczak B. J. Mol. Catal. B: Enzym. 2004, 29: 99

<A NAME="RD15807ST-7F">7f</A> 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

<A NAME="RD15807ST-7G">7g</A> Stowasser B. Budt KH. Jian-Qi L. Peyman A. Ruppert D. Tetrahedron Lett. 1992, 33: 6625

<A NAME="RD15807ST-7H">7h</A> Zheng X. Nair V. Tetrahedron 1999, 55: 11803

<A NAME="RD15807ST-7I">7i</A> 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

<A NAME="RD15807ST-7J">7j</A> Patel DV. Rielly-Gauvin K. Ryono DE. Tetrahedron Lett. 1990, 31: 5591

<A NAME="RD15807ST-8">8</A> Fields SC. Tetrahedron 1999, 55: 12237

<A NAME="RD15807ST-9">9</A> Kaboudin B. Tetrahedron Lett. 2003, 44: 1051

<A NAME="RD15807ST-10">10</A> Firouzabadi H. Iranpoor N. Sobhani S. Synth. Commun. 2004, 34: 1463

<A NAME="RD15807ST-10">10</A> Firouzabadi H. Iranpoor N. Sobhani S. Tetrahedron Lett. 2002, 43: 477

<A NAME="RD15807ST-10">10</A> Kaboudin B. Nazari R. Synth. Commun. 2001, 31: 2245

<A NAME="RD15807ST-11">11</A> Eymery F. Lorga B. Savignac P. Tetrahedron 1999, 55: 2671

<A NAME="RD15807ST-12">12</A> Firouzabadi H. Iranpoor N. Sobhani S. Amoozgar Z. Synthesis 2004, 1771

<A NAME="RD15807ST-13">13</A> Evans DA. Hurst KM. Takacs JM. J. Am. Chem. Soc. 1978, 100: 3467

<A NAME="RD15807ST-14">14</A> Texier-Boullet F. Foucaud A. Synthesis 1982, 916

<A NAME="RD15807ST-15">15</A> Texier-Boullet F. Lequitte M. Tetrahedron Lett. 1986, 27: 3515

<A NAME="RD15807ST-16">16</A> Azizi N. Saidi MR. Phosphorus, Sulfur Silicon Relat. Elem. 2003, 178: 1255

<A NAME="RD15807ST-17">17</A> Heydari A. Arefi A. Khaksar S. Tajbakhsh M. Catal. Commun. 2006, 7: 98

<A NAME="RD15807ST-18">18</A> Alexander CW. Albiniak PA. Gibson LR. Phosphorus, Sulfur Silicon Relat. Elem. 2000, 167: 205

<A NAME="RD15807ST-19">19</A> Saito B. Egami H. Katsuki T. J. Am. Chem. Soc. 2007, 129: 1978

<A NAME="RD15807ST-20">20</A> Dodda R. Zhao CG. Org. Lett. 2006, 8: 4911

<A NAME="RD15807ST-21">21</A> Yokomatsu T. Yamagishi T. Shibuya S. Tetrahedron: Asymmetry 1993, 4: 1779

<A NAME="RD15807ST-22A">22a</A> Goldeman W. Soroka M. Synthesis 2006, 3019

<A NAME="RD15807ST-22B">22b</A> Mizyuk VL. Cherepanova EG. Pudovik MA. Zhurnal Obshchei Khimii 1980, 50: 1878

<A NAME="RD15807ST-23">23</A> Sum V. Kee TP. J. Chem. Soc., Perkin Trans. 1 1993, 2701

<A NAME="RD15807ST-24">24</A> Gancarz R. Gancarz I. Walkowiak U. Phosphorus, Sulfur Silicon Relat. Elem. 1995, 104: 45

<A NAME="RD15807ST-25">25</A> Ko S. Yao C.-F. Tetrahedron Lett. 2006, 47: 8827

<A NAME="RD15807ST-26A">26a</A> Tian Q. Zhang S. Yu Q. He M.-B. Yang J.-S. Tetrahedron 2007, 63: 2142

<A NAME="RD15807ST-26B">26b</A> Sabou R. Hoelderich WF. Ramprasad D. Weinand R. J. Catal. 2005, 232: 34

<A NAME="RD15807ST-26C">26c</A> Yadav JS. Subba Reddy BV. Vishnumurthy P. Tetrahedron Lett. 2005, 46: 1311

<A NAME="RD15807ST-26D">26d</A> Honkela ML. Root A. Lindblad M. Krause AOI. Appl. Catal. A 2005, 295: 216

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).

<A NAME="RD15807ST-28">28</A> He A. Yan B. Thanavaro A. Spilling CD. Rath NP. J. Org. Chem. 2004, 69: 8643