HClO4-SiO2 as
a Novel and Recyclable Catalyst for the Phospha-Michael Addition
of Phosphorous Nucleophiles to α,β-Unsaturated
Malonates

Sara Sobhani; Soodabeh Rezazadeh

doi:10.1055/s-0029-1220069

LETTER

HClO₄-SiO₂ as a Novel and Recyclable Catalyst for the Phospha-Michael Addition of Phosphorous Nucleophiles to α,β-Unsaturated Malonates

Sara Sobhani*, Soodabeh Rezazadeh
Department of Chemistry, College of Sciences, Birjand University, Birjand 414, Iran
Fax: +98(561)2502009; e-Mail: ssobhani@birjand.ac.ir; e-Mail: sobhanisara@yahoo.com;

Abstract

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Abstract

An efficient synthesis of β-phosphono malonates via phospha-Michael addition of phosphorous nucleophiles to α,β-unsaturated malonates in the presence of HClO₄-SiO₂ as a new and recyclable catalyst is described.

Key words

silica-supported perchloric acid - phospha-Michael addition - β-phosphono malonates

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References

References and Notes

<A NAME="RD37309ST-1A">1a</A> Allen MC. Fuhrer W. Tuck B. Wade R. Wood JM. J. Med. Chem. 1989, 32: 1652

<A NAME="RD37309ST-1B">1b</A> Patel DV. Rielly-Gauvin K. Ryono DE. Tetrahedron Lett. 1990, 31: 5587

<A NAME="RD37309ST-1C">1c</A> Stowasser B. Budt KH. Li JQ. Peyman A. Ruppert D. Tetrahedron Lett. 1992, 33: 6625

<A NAME="RD37309ST-2">2</A> Kafarski P. Lejczak B. Phosphorus, Sulfur Silicon Relat. Elem. 1991, 63: 1993

<A NAME="RD37309ST-3A">3a</A> Baylis EK. Campbell CD. Dingwall JG. J. Chem. Soc., Perkin Trans. 1 1984, 2845

<A NAME="RD37309ST-3B">3b</A> Atherton FR. Hassal CH. Lambert RW. J. Med. Chem. 1986, 29: 29

<A NAME="RD37309ST-4">4</A> Maryanoff BE. Reitz AB. Chem. Rev. 1986, 86: 863

<A NAME="RD37309ST-5A">5a</A> Pudovik AN. Konovalova IV. Synthesis 1979, 81

<A NAME="RD37309ST-5B">5b</A> Enders D. Saint-Dizier A. Lannou MI. Lenzen A. Eur. J. Org. Chem. 2006, 29

<A NAME="RD37309ST-6A">6a</A> Miller RC. Bradley JS. Hamilton LA. J. Am. Chem. Soc. 1956, 78: 5299

<A NAME="RD37309ST-6B">6b</A> Bodalski R. Pietrusiewicz K. Tetrahedron Lett. 1972, 4209

<A NAME="RD37309ST-6C">6c</A> Simoni D. Invidiata FP. Manferdini M. Lampronti I. Rondanin R. Roberti M. Pollini GP. Tetrahedron Lett. 1998, 39: 7615

<A NAME="RD37309ST-7">7</A> Green K. Tetrahedron Lett. 1989, 30: 4807

<A NAME="RD37309ST-8">8</A> Hindersinn RR. Ludington RS. J. Org. Chem. 1965, 30: 4020

<A NAME="RD37309ST-9">9</A> Stockland RA. Taylor RI. Thompson LE. Patel PB. Org. Lett. 2005, 7: 851

<A NAME="RD37309ST-10A">10a</A> Shulyupin MO. Kazankova MA. Beletskaya IP. Org. Lett. 2002, 4: 761

<A NAME="RD37309ST-10B">10b</A> Xu Q. Han L.-B. Org. Lett. 2006, 8: 2099

<A NAME="RD37309ST-11A">11a</A> Semenzin D. Etemad-Moghadam G. Albouy D. Diallo O. Koenig M. J. Org. Chem. 1997, 62: 2414

<A NAME="RD37309ST-11B">11b</A> Han L.-B. Zhao C.-Q. J. Org. Chem. 2005, 70: 10121

<A NAME="RD37309ST-12A">12a</A> Solid Supports and Catalysts in Organic Synthesis Smith K. Prentice Hall; New York: 1992.

<A NAME="RD37309ST-12B">12b</A> Corma A. Garcia H. Adv. Synth. Catal. 2006, 348: 1391

<A NAME="RD37309ST-13A">13a</A> Chakraborti AK. Gulhane R. Chem. Commun. 2003, 1896

<A NAME="RD37309ST-13B">13b</A> Chakraborti AK, and Gulhane R. inventors; Indian Patent, 266/DEL/2003.

<A NAME="RD37309ST-14">14</A> Kantevair S. Bantu R. Nagarapu L. J. Mol. Catal. A: Chem. 2007, 269: 53

<A NAME="RD37309ST-15">15</A> Bigdeli MA. Heravi MM. Mahdavinia GH. J. Mol. Catal. A: Chem. 2007, 275: 25

<A NAME="RD37309ST-16">16</A> Das B. Damodar K. Chowdhury N. Kumar RA. J. Mol. Catal. A: Chem. 2007, 274: 148

<A NAME="RD37309ST-17">17</A> Das B. Venkateswarlu K. Majhi A. Reddy MR. Reddy KN. Rao YK. Ravikumar K. Sridhar B. J. Mol. Catal. A: Chem. 2006, 246: 276

<A NAME="RD37309ST-18">18</A> Das B. Venkateswarlu K. Suneel K. Majhi A. Tetrahedron Lett. 2007, 48: 5371

<A NAME="RD37309ST-19">19</A> Khatik GL. Sharma G. Kumar R. Chakraborti AK. Tetrahedron 2007, 63: 1200

<A NAME="RD37309ST-20">20</A> Kumar A. Sharma S. Maurya RA. Tetrahedron Lett. 2009, 50: 5937

<A NAME="RD37309ST-21A">21a</A> Sobhani S. Tashrifi Z. Synth. Commun. 2009, 39: 120

<A NAME="RD37309ST-21B">21b</A> Sobhani S. Tashrifi Z. Heteroatom Chem. 2009, 20: 109

<A NAME="RD37309ST-21C">21c</A> Sobhani S. Safaei E. Asadi M. Jalili F. J. Organomet. Chem. 2008, 693: 3313

<A NAME="RD37309ST-21D">21d</A> Sobhani S. Safaei E. Asadi M. Jalili F. Tashrifi Z. J. Porphyrins Phthalocyanines 2008, 12: 849

<A NAME="RD37309ST-21E">21e</A> Sobhani S. Vafaee A. Tetrahedron 2009, 65: 7691

<A NAME="RD37309ST-21F">21f</A> Sobhani S. Vafaee A. Synthesis 2009, 1909

<A NAME="RD37309ST-21G">21g</A> Sobhani S. Vafaee A. J. Iran. Chem. Soc. 2010, 7: 227

<A NAME="RD37309ST-21H">21h</A> Sobhani S. Tashrifi Z. Tetrahedron 2010, 66: 1429

<A NAME="RD37309ST-21I">21i</A> Sobhani S. Faal Maleki M. Synlett 2010, 383

<A NAME="RD37309ST-22">22</A> Variot G. Collect A. Acros Org. Acta 1995, 1: 40

<A NAME="RD37309ST-23A">23a</A> Hosseini-Sarvari M. Etemad S. Tetrahedron 2008, 64: 5519

<A NAME="RD37309ST-23B">23b</A> Mahran MR. Abdou WM. Heteroatom. Chem. 1992, 3: 93

General Procedure for the Synthesis of β-Phosphono Malonates (2a-t): HClO₄-SiO₂ (0.03 mmol, 0.057 g, 0.52 mmol/g) was added to a mixture of α,β-unsaturated malonates 1a-t (1 mmol) and P(OEt)₃ (1 mmol). The mixture was stirred and monitored by TLC. After completion of the reaction, the reaction mixture was diluted with EtOAc and filtered. Evaporation of the solvent under reduced pressure gave the crude products. The pure products, 2a-t, were obtained by chromatography on silica, eluting with n-hexane-EtOAc (1:1).

(1-Phenyl-2,2-dicyanoethyl) Phosphonic Acid Diethyl Ester (2a)
^¹H NMR (CDCl₃): δ = 1.11 (t, 3 H, ^³ J _HH = 6.8 Hz), 1.33 (t, 3 H, ^³ J _HH = 7.0 Hz), 3.65 (dd, 1 H, ^³ J _HH = 8.0, ^² J _HP = 21.0 Hz), 3.91-4.21 (m, 4 H), 4.55 (t, 1 H, ^³ J _HH = 8.3 Hz), 7.43 (s, 5 H). ^¹³C NMR (CDCl₃): δ = 16.1 (d, ^³ J _CP = 5.6 Hz), 16.2 (d, ^³ J _CP = 5.6 Hz), 25.5, 44.6 (d, ^¹ J _CP = 144.0 Hz), 63.4 (d, ^² J _CP = 7.5 Hz), 64.4 (d, ^² J _CP = 7.0 Hz), 111.1 (d, ^³ J _CP = 12.5 Hz), 111.3 (d, ^³ J _CP = 10.0 Hz), 129.2, 129.3, 129.4, 129.8. ^³¹P NMR (CDCl₃): δ = 20.04. MS (70 eV): m/z = 292 [M⁺], 155 [M⁺ - P(O)(OEt)₂].
[1-(2-Chlorophenyl)-2,2-dicyanoethyl] Phosphonic Acid Diethyl Ester (2b)
^¹H NMR (CDCl₃): δ = 1.11 (t, 3 H, ^³ J _HH = 7.0 Hz), 1.36 (t, 3 H, ^³ J _HH = 7.0 Hz), 3.75-4.30 (m, 4 H), 4.46 (dd, 1 H, ^³ J _HH = 8.2, ^² J _HP = 21.2 Hz), 4.61 (t, 1 H, ^³ J _HH = 8.5 Hz), 7.35 (d, 2 H, ^³ J _HH = 4.0 Hz), 7.47 (s, 1 H), 7.75 (d, 1 H, ^³ J _HH = 5.3 Hz). ^¹³C NMR (CDCl₃): δ = 16.0 (d, ^³ J _CP = 6.3 Hz), 16.2 (d, ^³ J _CP = 5.6 Hz), 24.9, 39.4 (d, ^¹ J _CP = 144.6 Hz), 63.6 (d, ^² J _CP = 7.5 Hz), 64.4 (d, ^² J _CP = 6.9 Hz), 110.9 (d, ^³ J _CP = 5.6 Hz), 111.1, 127.8, 128.6, 129.6, 130.6, 135.1. ^³¹P NMR (CDCl₃): δ = 19.47. MS (70 eV): m/z = 326 [M⁺], 328 [M⁺ + 2], 189 [M⁺ - P(O)(OEt)₂], 191 [(M⁺ + 2) - P(O)(OEt)₂].
[1-(4-Chlorophenyl)-2,2-dicyanoethyl] Phosphonic Acid Diethyl Ester (2d)
^¹H NMR (CDCl₃): δ = 1.16 (t, 3 H, ^³ J _HH = 7.0 Hz), 1.33 (t, 3 H, ^³ J _HH = 7.0 Hz), 3.62 (dd, 1 H, ^³ J _HH = 7.5 Hz, ^² J _HP = 21.5 Hz), 3.82-4.19 (m, 4 H), 4.55 (t, 1 H, ^³ J _HH = 7.7 Hz), 7.42 (s, 4 H). ^¹³C NMR (CDCl₃): δ = 16.1 (d, ^³ J _CP = 5.0 Hz), 16.2 (d, ^³ J _CP = 5.6 Hz), 25.5, 43.9 (d, ^¹ J _CP = 144.7 Hz), 63.5 (d, ^² J _CP = 7.0 Hz), 64.4 (d, ^² J _CP = 7.0 Hz), 111.0 (d, ^³ J _CP = 11.9 Hz), 111.2 (d, ^³ J _CP = 11.3 Hz), 128.8, 129.6, 130.7, 135.7. ^³¹P NMR (CDCl₃): δ = 19.42. MS (70 eV): m/z = 326 [M⁺], 328 [M⁺ + 2], 189 [M⁺ - P(O)(OEt)₂], 191 [(M⁺ + 2) - P(O)(OEt)₂].
[1-(Naphthalen-2-yl)-2,2-dicyanoethyl] Phosphonic Acid Diethyl Ester (2j)
^¹H NMR (CDCl₃): δ = 1.08 (t, 3 H, ^³ J _HH = 7.0 Hz), 1.36 (t, 3 H, ^³ J _HH = 7.0 Hz), 3.65-4.22 (m, 5 H), 4.66 (t, 1 H, ^³ J _HH = 8.5 Hz), 7.52-7.58 (m, 3 H), 7.87-7.96 (m, 4 H). ^¹³C NMR (CDCl₃): δ = 16.1 (d, ^³ J _CP = 5.6 Hz), 16.2 (d, ^³ J _CP = 6.2 Hz), 25.7, 44.8 (d, ^¹ J _CP = 144.0 Hz), 63.4 (d, ^² J _CP = 7.5 Hz), 64.4 (d, ^² J _CP = 7.0 Hz), 111.2 (d, ^³ J _CP = 13.2 Hz), 111.3 (d, ^³ J _CP = 8.2 Hz), 125.9, 126,9, 127.2, 127.6, 127.7, 127.8, 128.2, 129.2, 129.4, 133.3. ^³¹P NMR (CDCl₃): δ = 19.95.
[1-(Furan-2-yl)-2,2-dicyanoethyl] Phosphonic Acid Diethyl Ester (2k)
^¹H NMR (CDCl₃): δ = 1.24-1.37 (m, 6 H), 3.87 (dd, 1 H, ^³ J _HH = 6.5 Hz, ^² J _HP = 22.7 Hz), 3.98-4.23 (m, 4 H), 4.51 (t, 1 H, ^³ J _HH = 8.7 Hz), 6.44 (s, 1 H), 6.62 (s, 1 H), 7.49 (s, 1 H).
^¹³C NMR (CDCl₃): δ = 16.1, 16.2, 24.3, 39.1 (d, ^¹ J _CP = 147.1 Hz), 63.9 (d, ^² J _CP = 6.9 Hz), 64.2 (d, ^² J _CP = 6.9 Hz), 110.9 (d, ^³ J _CP = 9.4 Hz), 111.1 (d, ^³ J _CP = 11.9 Hz), 111.3, 111.7, 143.2, 144.0.^³¹P NMR (CDCl₃): δ = 19.88. MS (70 eV): m/z = 282 [M⁺], 145 [M⁺ -P(O)(OEt)₂].
[1-(Pyridin-3-yl)-2,2-dicyanoethyl] Phosphonic Acid Diethyl Ester (2m)
^¹H NMR (CDCl₃): δ = 1.18 (t, 3 H, ^³ J _HH = 6.8 Hz), 1.33 (t, 3 H, ^³ J _HH = 7.0 Hz), 3.65 (dd, 1 H, ^³ J _HH = 6.8 Hz, ^² J _HP = 21.6 Hz), 3.92-4.21 (m, 4 H), 4.63 (t, 1 H, ^³ J _HH = 8.5 Hz), 7.39 (t, 1 H, ^³ J _HH = 6.5 Hz), 7.95 (d, 1 H, ^³ J _HH = 6.5 Hz), 8.67 (s, 2 H). ^¹³C NMR (CDCl₃): δ = 16.1 (d, ^³ J _CP = 5.0 Hz), 16.2 (d, ^³ J _CP = 5.0 Hz), 25.3, 42.1 (d, ^¹ J _CP = 144.6 Hz), 63.8 (d, ^² J _CP = 7.0 Hz), 64.5 (d, ^² J _CP = 7.0 Hz), 110.8 (d, ^³ J _CP = 10.7 Hz), 111.0 (d, ^³ J _CP = 11.9 Hz), 124.0, 126,7, 136.5, 150.5, 150.8. ^³¹P NMR (CDCl₃): δ = 19.03. MS (70 eV): m/z = 293 [M⁺], 156 [M⁺ - P(O)(OEt)₂].

HClO4-SiO2 as a Novel and Recyclable Catalyst for the Phospha-Michael Addition of Phosphorous Nucleophiles to α,β-Unsaturated Malonates

HClO₄-SiO₂ as a Novel and Recyclable Catalyst for the Phospha-Michael Addition of Phosphorous Nucleophiles to α,β-Unsaturated Malonates