A Facile Anchoring of the Bisphosphonate Moiety into Alcohols and Phenols through Copper Carbenoid Mediated O-H Insertion Reaction

Delphine Lecerclé; Frédéric Taran

doi:10.1055/s-2007-984535

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Synlett 2007(12): 1863-1868
DOI: 10.1055/s-2007-984535

LETTER

A Facile Anchoring of the Bisphosphonate Moiety into Alcohols and Phenols through Copper Carbenoid Mediated O-H Insertion Reaction

Delphine Lecerclé, Frédéric Taran*
CEA, iBiTecS, Service de Chimie Bioorganique et de Marquage, 91191 Gif sur Yvette, France
Fax: +33(1)69087991; e-Mail: Frederic.taran@cea.fr;

Further Information

Publication History

Received 19 April 2007
Publication Date:
27 June 2007 (online)

Abstract
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Abstract

A straightforward procedure ensuring the anchoring of bisphosphonate moiety into alcohols or phenols is described. The method uses a bisphosphonate-metal-carbenoid O-H insertion reaction for which copper(II) triflate was found to be an efficient catalyst.

Key words

carbenoids - insertions - copper - rhodium - phosphorus

References and Notes

1a Widler L. Jaeggi KA. Glatt M. Müller K. Bachmann R. Bisping M. Born AR. Corseti R. Guiglia G. Jeker H. Klein R. Ramseier U. Schmid J. Schreiber G. Seltenmeyer Y. Green JR. J. Med. Chem. 2002, 45: 3721

Crossref Google Scholar
1b Rodan GA. Annu. Rev. Pharmacol. Toxicol. 1998, 38: 375

Crossref Google Scholar
1c Prestwood KM. Pilbeam CC. Raisz LG. Annu. Rev. Med. 1995, 46: 249

Crossref Google Scholar
1d Mundy GR. Annu. Rev. Med. 2002, 53: 337

Crossref Google Scholar
2 Russel RGG. Rogers MJ. Br. J. Rheumatol. 1997, 36: 10 ; Suppl. 1

Google Scholar
3a Pecherstorfer M. Herrmann Z. Body J.-J. Manegold C. Degardin M. Clemens MR. Thurlimann B. Tubiana-Hulin M. Steinhauer EU. J. Clin. Oncol. 1996, 14: 268

Crossref Google Scholar
3b Clezardin P. Fournier P. Boissier S. Peyruchaud O. Curr. Med. Chem. 2003, 10: 173

Crossref Google Scholar
3c Guenin E. Ledoux D. Oudar O. Lecouvet M. Kraemer M. Anticancer Res. 2005, 25: 1139

Crossref Google Scholar
3d Wilheim M. Kunzman V. Eckstein S. Reimer P. Weissinger F. Ruediger T. Tony HP. Blood 2003, 102: 200

Crossref Google Scholar
4 Kubicek V. Rudocsky J. Kotek J. Hermann P. Vander Elst L. Muller RN. Kollar ZI. Wolterbeek HThh. Peters JA. Lukes I. J. Am. Chem. Soc. 2005, 127: 16477

Crossref Google Scholar
5a Wang L. Yang Z. Gao J. Xu K. Gu H. Zhang B. Zhang X. Xu B. J. Am. Chem. Soc. 2006, 128: 13358

Google Scholar
5b Sawicki M. Siaugue JM. Jacopin C. Moulin C. Bailly T. Burgada R. Meunier S. Baret P. Pierre JL. Taran F. Chem. Eur. J. 2005, 11: 3689

Google Scholar
5c Challeix V. Lecouvey M. Tetrahedron Lett. 2007, 48: 703

Google Scholar
5d Burgada R. Bailly T. Prangé T. Lecouvey M. Tetrahedron Lett. 2007, 26: 2315

Google Scholar
6a Sturz G. Appéré G. Breistol K. Fodstad O. Schwartsmann G. Hendriks HR. Eur. J. Med. Chem. 1992, 27: 825

Crossref Google Scholar
6b Herczegh P. Buxton YB. McPherson JC. Kovacs-Kulyassa A. Brewer PD. Sztaricskai F. Stroebel GG. Plowman KM. Farcasiu D. Hartmann JF. J. Med. Chem. 2002, 45: 2338

Crossref Google Scholar
6c Kultyshev RG. Liu J. Liu S. Tjarks W. Soloway AH. Shore SG. J. Am. Chem. Soc. 2002, 124: 2614

Crossref Google Scholar
6d Gil C. Han Y. Opas EE. Rodan GA. Ruel RJ. Seedor JG. Tyler PC. Young RN. Bioorg. Med. Chem. 1999, 7: 901

Crossref Google Scholar
7a Mallard I. Benech JM. Lecouvey M. Leroux Y. Phosphorus, Sulfur Silicon Relat. Elem. 2000, 162: 15

Crossref Google Scholar
7b Gouault-Bironneau S. Deprèle S. Sutor A. Montchamp J.-P. Org. Lett. 2005, 7: 5909

Crossref Google Scholar
7c Lecouvey M. Mallard I. Bailly T. Burgada R. Leroux Y. Tetrahedron Lett. 2001, 42: 8475

Crossref Google Scholar
7d Guenin E. Degache E. Liquier J. Lecouvey M. Eur. J. Org. Chem. 2004, 2983

Crossref Google Scholar
7e Stepinski DC. Nelson DW. Zalupski PR. Herlinger AW. Tetrahedron 2001, 57: 8637

Crossref Google Scholar
7f Migianu E. Guénin E. Lecouvey M. Synlett 2005, 425

Crossref Google Scholar
7g Ruzziconi R. Ricci G. Gioiello A. Couthon-Gourvès H. Gourvès J.-P. J. Org. Chem. 2003, 68: 736

Crossref Google Scholar
7h Migianu E. Mallard I. Bouchemal N. Lecouvey M. Tetrahedron Lett. 2004, 45: 4511

Crossref Google Scholar
8 Lecerclé D. Sawicki M. Taran F. Org. Lett. 2006, 8: 4283

Crossref Google Scholar
9a Haigh D. Tetrahedron 1994, 50: 3177

Crossref Google Scholar
9b Wood HB. Buser H.-P. Ganem B. J. Org. Chem. 1992, 57: 178

Crossref Google Scholar
10a Wong FM. Wang J. Hengge AC. Wu W. Org. Lett. 2007, 9: 1663

Crossref Google Scholar
10b Nowlan DT. Gregg TM. Davies HML. Singleton DA. J. Am. Chem. Soc. 2003, 125: 15902

Crossref Google Scholar
11a Cox GG. Kulagowski JJ. Moody CJ. Sie E.-BHB. Synlett 1992, 975

Crossref Google Scholar
11b Cox GG. Miller DJ. Moody CJ. Sie E.-BHB. Tetrahedron 1994, 50: 3195

Crossref Google Scholar
For examples of the use of Cu(OTf)₂ in organic synthesis, see:
12a Jones S. Smanmoo C. Org. Lett. 2005, 7: 3271

Crossref Google Scholar
12b Bayer A. Endeshaw MM. Gautun OR. J. Org. Chem. 2004, 69: 7198

Crossref Google Scholar
12c Endeshaw MM. Bayer A. Hansen LK. Gautun O. Eur. J. Org. Chem. 2006, 5249

Crossref Google Scholar
12d Hertweck C. J. Prakt. Chem. 2000, 342: 316

Crossref Google Scholar

13

General Procedure
To a solution of diazo bisphosphonate 1a (100 mg, 0.318 mmol) and alcohol (0.350 mmol) in 6 mL of anhyd toluene was added Cu(OTf)₂ (1.2 mg, 0.003 mmol). The mixture was heated under reflux for 8 or 12 h and then evaporated under reduced pressure. The residue was purified directly by flash chromatography on silica column (acetone-CH₂Cl₂, 1:1) to afford the desired product.
All new compounds have been characterized by ¹H NMR, ¹³C NMR, ³¹P NMR, IR, and mass spectroscopy.
Selected Data:
Compound 5b: ¹H NMR (400 MHz, CDCl₃): δ = 1.29 (t, J = 7.2 Hz, 6 H), 1.31 (t, J = 7.2 Hz, 6H), 4.04 (t, J = 17.8 Hz, 1 H), 4.08-4.20 (m, 8 H), 4.80 (s, 2 H), 7.26-7.38 (m, 5 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 16.32-16.41 (m), 63.16 (d, J = 3.0 Hz), 63.19 (d, J = 3.0 Hz), 63.31 (d, J = 3.0 Hz), 63.34 (d, J = 3.0 Hz), 71.50 (t, J = 157.0 Hz), 75.58 (t, J = 5.0 Hz), 128.16, 1128.26, 128.67, 136.34 ppm. ³¹P NMR (160 MHz, CDCl₃): δ = 16.09 (s, 2 P) ppm. MS (ESI/TOF): m/z = 395 [M + H]⁺.
Compound 5c: ¹H NMR (400 MHz, CDCl₃): δ = 1.29 (t, J = 7.2 Hz, 6 H), 1.32 (t, J = 7.2 Hz, 6 H), 4.18-4.30 (m, 8 H), 4.89 (t, J = 17.8 Hz, 1 H), 4.80 (s, 2 H), 7.02 (t, J = 7.6 Hz, 1 H), 7.09 (d, J = 7.6 Hz, 2 H), 7.29 (t, J = 7.6 Hz, 2 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 16.26 (d, J = 2.9 Hz), 16.29 (d, J = 2.9 Hz), 16.36 (d, J = 2.9 Hz), 16.39 (d, J = 2.9 Hz), 63.50 (d, J = 3.2 Hz), 63.53 (d, J = 3.2 Hz), 63.87 (d, J = 3.2 Hz), 63.90 (d, J = 3.2 Hz), 72.35 (t, J = 157.0 Hz), 116.23, 122.64, 129.45, 158.71 (t, J = 4.5 Hz) ppm. ³¹P NMR (160 MHz, CDCl₃): δ = 14.51 (s, 2 P) ppm. MS (ESI/TOF): m/z = 381 [M + H]⁺.
Compound 5d: ¹H NMR (400 MHz, CDCl₃): δ = 1.30 (t, J = 6.8 Hz, 12 H), 4.06-4.25 (m, 11 H), 5.19-5.30 (m, 2 H), 5.79-5.88 (m, 1 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 16.24-16.31, 63.29 (d, J = 3.0 Hz), 63.32 (d, J = 3.0 Hz), 63.52 (d, J = 3.0 Hz), 63.55 (d, J = 3.0 Hz), 70.87 (t, J = 157.0 Hz), 74.72 (t, J = 4.7 Hz), 119.19, 133.13 ppm. ³¹P NMR (160 MHz, CDCl₃): δ = 16.29 (s, 2 P) ppm. MS (ESI/TOF): m/z = 345 [M + H]⁺.
Compound 5e: ¹H NMR (400 MHz, CDCl₃): δ = 1.31 (t, J = 7.2 Hz, 6 H), 1.32 (t, J = 7.2 Hz, 6 H), 4.10 (t, J = 17.2 Hz, 1 H), 4.10-4.24 (m, 8 H), 4.77 (s, 2 H), 6.34 (dd, J = 3.2, 1.2 Hz, 1 H), 6.40 (d, J = 3.2 Hz, 1 H), 7.41 (d, J = 1.2 Hz, 1 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 16.30-16.41 (m), 63.17 (d, J = 3.0 Hz), 63.20 (d, J = 3.0 Hz), 63.42 (d, J = 3.0 Hz), 63.46 (d, J = 3.0 Hz), 66.11 (t, J = 5.2 Hz), 70.15 (t, J = 157.0 Hz), 110.35, 111.47, 143.37, 149.92 ppm. ³¹P NMR (160 MHz, CDCl₃): δ = 15.93 (s, 2 P) ppm. HRMS: m/z calcd for C₁₄H₂₆O₈P₂Na: 407.1001; found: 407.1014.
Compound 5f: ¹H NMR (400 MHz, CDCl₃): δ = 0.79 (s, 3 H), 1.15 (s, 3 H), 1.23-1.29 (m, 2 H), 1.31 (t, J = 7.2 Hz, 6 H), 1.32 (t, J = 7.2 Hz, 6 H), 1.58 (m, J = 8.0 Hz, 1 H), 1.67-1.76 (m, 2 H), 1.80-1.82 (m, 1 H), 1.86-1.88 (m, 1 H), 1.96-1.99 (m, 1 H), 2.28 (qt, J = 7.6 Hz, 1 H), 3.51 (d, J = 7.2 Hz, 2 H), 3.85 (t, J = 17.8 Hz, 1 H), 4.10-4.21 (m, 8 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 16.30-16.41 (m), 18.08, 20.04, 23.44, 23.96, 26.52, 35.97, 38.97, 40.74, 42.22, 62.97-63.17 (m), 73.47 (t, J = 157.0 Hz), 79.15 (t, J = 4.3 Hz) ppm. ³¹P NMR (160 MHz, CDCl₃): δ = 16.21 (s, 2 P) ppm. MS (ESI/TOF): m/z = 441 [M + H]⁺.

Compound 5h: ¹H NMR (400 MHz, CDCl₃): δ = 1.27-1.34 (m, 15 H), 1.41 (s, 3 H), 3.85 (dd, J = 18.0 16.0 Hz, 1 H), 3.96-4.03 (m, 2 H), 4.06-4.22 (m, 8 H), 4.59 (s, 1 H), 4.77 (d, J = 5.6 Hz, 1 H), 4.80 (d, J = 5.6 Hz, 1 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 16.66-16.78 (m), 23.91, 27.06, 63.67 (d, J = 6.6 Hz), 63.79 (d, J = 6.6 Hz), 64.02 (d, J = 6.6 Hz), 73.50 (dd, J = 3.7, 5.7 Hz), 73.89 (t, J = 157.0 Hz), 75.80, 78.39, 80.82, 113.48, 174.38 ppm. ³¹P NMR (160 MHz, CDCl₃): δ = 14.41 (d, J = 28 Hz, 1 P), 15.89 (d, J = 28 Hz, 1 P) ppm. HRMS: m/z calcd for C₁₇H₃₂O₁₁P₂Na: 497.1318; found: 497.1326.
Compound 5i: ¹H NMR (400 MHz, CDCl₃): δ = 1.23 (t, J = 7.2 Hz, 6 H), 1.26 (t, J = 7.2 Hz, 6 H), 3.08 (s, 3 H), 3.65 (t, J = 5.4 Hz, 2 H), 3.89 (t, J = 18.0 Hz, 1 H), 3.95 (t, J = 5.4 Hz, 2 H), 4.06-4.18 (m, 8 H), 6.69 (d, J = 8.8 Hz, 2 H), 7.67 (d, J = 8.8 Hz, 2 H), 9.68 (s, 1 H) ppm ¹³C NMR (100 MHz, CDCl₃): δ = 16.30-16.35 (m), 39.03, 51.68, 63.18-63.32 (m), 71.97 (t, J = 4.5 Hz), 73.53 (t, J = 157.0 Hz), 110.93, 125.21, 131.90, 153.36, 190.09 ppm. ³¹P NMR (160 MHz, CDCl₃): δ = 15.72 (s, 2 P) ppm. MS (ESI/TOF): m/z = 466 [M + H]⁺.
Compound 5j: ¹H NMR (400 MHz, CDCl₃): δ = 1.32 (t, J = 7.2 Hz, 12 H), 1.56 (s, 6 H), 1.64 (s, 3 H), 1.91-1.95 (m, 2 H), 1.99-2.10 (m, 6 H), 3.99 (t, J = 17.6 Hz, 1 H), 4.16-4.26 (m, 8 H), 4.30 (d, J = 7.2 Hz, 2 H), 5.03-5.08 (m, 2 H), 5.30 (t, J = 7.2 Hz, 1 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 15.86, 16.33-16.41 (m), 17.56, 25.58, 26.21, 26.60, 39.58, 63.06 (d, J = 3.0 Hz), 63.09 (d, J = 3.0 Hz), 63.28 (d, J = 3.0 Hz), 63.31 (d, J = 3.0 Hz), 69.90 (t, J = 4.7 Hz), 70.62 (t, J = 157.0 Hz), 119.28, 123.54, 124.17, 131.19, 135.33, 142.83 ppm. ³¹P NMR (160 MHz, CDCl₃): δ = 16.52 (s, 2 P) ppm. MS (ESI/TOF): m/z = 509 [M + H]⁺.
Compound 5k: ¹H NMR (400 MHz, CDCl₃): δ = 1.30 (t, J = 7.2 Hz, 6 H), 1.31 (t, J = 7.2 Hz, 6 H), 4.19-4.34 (m, 8 H), 4.89 (t, J = 17.2 Hz, 1 H), 7.15 (d, J = 8.8 Hz, 2 H), 7.29 (t, J = 7.4 Hz, 2 H), 7.39 (t, J = 7.4 Hz, 2 H), 7.50 (d, J = 8.6 Hz, 2 H), 7.52 (d, J = 7.4 Hz, 2 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 16.30 (d, J = 3.0 Hz), 16.33 (d, J = 3.0 Hz), 16.39 (d, J = 3.0 Hz), 16.41 (d, J = 3.0 Hz), 63.54 (d, J = 3.0 Hz), 63.57 (d, J = 3.0 Hz), 63.87 (d, J = 3.0 Hz), 63.90 (d, J = 3.0 Hz), 72.55 (t, J = 157.0 Hz), 116.51, 126.71, 126.91, 128.09, 128.68, 135.70, 140.30, 158.25 (t, J = 4.5 Hz) ppm. ³¹P NMR (160 MHz, CDCl₃): δ = 14.41 (s, 2 P) ppm. MS (ESI/TOF): m/z = 457 [M + H]⁺.
Compound 5m: ¹H NMR (400 MHz, CDCl₃): δ = 1.33 (t, J = 7.2 Hz, 12 H), 3.55 (s, 3 H), 3.56-3.72 (m, 176.0 H), 3.79 (t, J = 4.8 Hz, 2 H), 3.91 (t, J = 4.8 Hz, 2 H), 4.08 (t, J = 17.6 Hz, 1 H), 4.18-4.26 (m, 8 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 16.4-16.44 (m), 58.96, 63.23 (d, J = 3.0 Hz), 63.26 (d, J = 3.0 Hz), 63.33 (d, J = 3.0 Hz), 63.36 (d, J = 3.0 Hz), 70.31-70.62 (m), 71.84, 73.43 (t, J = 157.0 Hz) ppm. ³¹P NMR (160 MHz, CDCl₃): δ = 15.99 (s, 2 P) ppm.