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

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Synlett 2010(10): 1485-1488
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;

Further Information

Publication History

Received 19 December 2009
Publication Date:
25 May 2010 (online)

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

References and Notes

1a Allen MC. Fuhrer W. Tuck B. Wade R. Wood JM. J. Med. Chem. 1989, 32: 1652

Google Scholar
1b Patel DV. Rielly-Gauvin K. Ryono DE. Tetrahedron Lett. 1990, 31: 5587

Google Scholar
1c Stowasser B. Budt KH. Li JQ. Peyman A. Ruppert D. Tetrahedron Lett. 1992, 33: 6625

Google Scholar
2 Kafarski P. Lejczak B. Phosphorus, Sulfur Silicon Relat. Elem. 1991, 63: 1993

Google Scholar
3a Baylis EK. Campbell CD. Dingwall JG. J. Chem. Soc., Perkin Trans. 1 1984, 2845

Google Scholar
3b Atherton FR. Hassal CH. Lambert RW. J. Med. Chem. 1986, 29: 29

Google Scholar
4 Maryanoff BE. Reitz AB. Chem. Rev. 1986, 86: 863

Google Scholar
5a Pudovik AN. Konovalova IV. Synthesis 1979, 81

Google Scholar
5b Enders D. Saint-Dizier A. Lannou MI. Lenzen A. Eur. J. Org. Chem. 2006, 29

Google Scholar
6a Miller RC. Bradley JS. Hamilton LA. J. Am. Chem. Soc. 1956, 78: 5299

Google Scholar
6b Bodalski R. Pietrusiewicz K. Tetrahedron Lett. 1972, 4209

Google Scholar
6c Simoni D. Invidiata FP. Manferdini M. Lampronti I. Rondanin R. Roberti M. Pollini GP. Tetrahedron Lett. 1998, 39: 7615

Google Scholar
7 Green K. Tetrahedron Lett. 1989, 30: 4807

Crossref Google Scholar
8 Hindersinn RR. Ludington RS. J. Org. Chem. 1965, 30: 4020

Crossref Google Scholar
9 Stockland RA. Taylor RI. Thompson LE. Patel PB. Org. Lett. 2005, 7: 851

Crossref PubMed Google Scholar
10a Shulyupin MO. Kazankova MA. Beletskaya IP. Org. Lett. 2002, 4: 761

Google Scholar
10b Xu Q. Han L.-B. Org. Lett. 2006, 8: 2099

Google Scholar
11a Semenzin D. Etemad-Moghadam G. Albouy D. Diallo O. Koenig M. J. Org. Chem. 1997, 62: 2414

Google Scholar
11b Han L.-B. Zhao C.-Q. J. Org. Chem. 2005, 70: 10121

Google Scholar
12a Solid Supports and Catalysts in Organic Synthesis Smith K. Prentice Hall; New York: 1992.

Google Scholar
12b Corma A. Garcia H. Adv. Synth. Catal. 2006, 348: 1391

Google Scholar
13a Chakraborti AK. Gulhane R. Chem. Commun. 2003, 1896

Google Scholar
13b Chakraborti AK, and Gulhane R. inventors; Indian Patent, 266/DEL/2003.
14 Kantevair S. Bantu R. Nagarapu L. J. Mol. Catal. A: Chem. 2007, 269: 53

Crossref Google Scholar
15 Bigdeli MA. Heravi MM. Mahdavinia GH. J. Mol. Catal. A: Chem. 2007, 275: 25

Crossref Google Scholar
16 Das B. Damodar K. Chowdhury N. Kumar RA. J. Mol. Catal. A: Chem. 2007, 274: 148

Crossref Google Scholar
17 Das B. Venkateswarlu K. Majhi A. Reddy MR. Reddy KN. Rao YK. Ravikumar K. Sridhar B. J. Mol. Catal. A: Chem. 2006, 246: 276

Crossref Google Scholar
18 Das B. Venkateswarlu K. Suneel K. Majhi A. Tetrahedron Lett. 2007, 48: 5371

Crossref Google Scholar
19 Khatik GL. Sharma G. Kumar R. Chakraborti AK. Tetrahedron 2007, 63: 1200

Crossref Google Scholar
20 Kumar A. Sharma S. Maurya RA. Tetrahedron Lett. 2009, 50: 5937

Crossref Google Scholar
21a Sobhani S. Tashrifi Z. Synth. Commun. 2009, 39: 120

Google Scholar
21b Sobhani S. Tashrifi Z. Heteroatom Chem. 2009, 20: 109

Google Scholar
21c Sobhani S. Safaei E. Asadi M. Jalili F. J. Organomet. Chem. 2008, 693: 3313

Google Scholar
21d Sobhani S. Safaei E. Asadi M. Jalili F. Tashrifi Z. J. Porphyrins Phthalocyanines 2008, 12: 849

Google Scholar
21e Sobhani S. Vafaee A. Tetrahedron 2009, 65: 7691

Google Scholar
21f Sobhani S. Vafaee A. Synthesis 2009, 1909

Google Scholar
21g Sobhani S. Vafaee A. J. Iran. Chem. Soc. 2010, 7: 227

Google Scholar
21h Sobhani S. Tashrifi Z. Tetrahedron 2010, 66: 1429

Google Scholar
21i Sobhani S. Faal Maleki M. Synlett 2010, 383

Google Scholar
22 Variot G. Collect A. Acros Org. Acta 1995, 1: 40

Google Scholar
23a Hosseini-Sarvari M. Etemad S. Tetrahedron 2008, 64: 5519

Google Scholar
23b Mahran MR. Abdou WM. Heteroatom. Chem. 1992, 3: 93

Google Scholar

24

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].