The Reduction of Aryl Diethyl Phosphate Esters with Lithium Di-tert-butylbiphenylide Radical Anion: Aromatic Hydrocarbons via the Deoxygenation of Phenols

Michael J. Lusch; Kevin R. Woller; Anthony M. Keller; Michael C. Turk

doi:10.1055/s-2005-861790

PAPER

The Reduction of Aryl Diethyl Phosphate Esters with Lithium Di-tert-butylbiphenylide Radical Anion: Aromatic Hydrocarbons via the Deoxygenation of Phenols

Michael J. Lusch*, Kevin R. Woller, Anthony M. Keller, Michael C. Turk
Department of Chemistry and Geology, Minnesota State University, Mankato, 242TN Trafton Science Center North, Mankato, MN 56001, USA
Fax: +1(507)3895625; e-Mail: michael.lusch@mnsu.edu;

Abstract

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Abstract

The reduction of aryl diethyl phosphate esters by lithium 4,4′-di-tert-butylbiphenylide (LiDTBB) in THF at 0 °C is described. The reactions can be carried out either stoichiometrically (3.0 equiv LiDTBB) or with only a catalytic amount of DTBB (0.25 equiv) in the presence of lithium (2.1-3.0 equiv) and the phosphate. Products are separated from DTBB by solubility differences, by acid/base vs. neutral extraction, or by flash chromatography.

Key words

reduction - phosphates - deoxygenation - phenols - arenes

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References

1a Cabri W. De Bernardinis S. Francalanci F. Penco S. J. Chem. Soc., Perkin Trans. 1 1990, 428

1b Takayama H. Kitajima M. Sakai S.-I. Heterocycles 1990, 30: 325

1c Engler TA. Reddy JP. Combrink KD. Vander Velde D. J. Org. Chem. 1990, 55: 1248

1d Peterson GA. Kunng F.-A. McCallum JS. Wulff WD. Tetrahedron Lett. 1987, 28: 1381

1e Wulff WD. McCallum JS. Kunng F.-A. J. Am. Chem. Soc. 1988, 110: 7419

For summaries of deoxygenation methods see the following and references cited therein:

2a Welch SC. Walters ME. J. Org. Chem. 1978, 43: 4797

2b Hussey BJ. Johnstone RAW. Entwistle ID. Tetrahedron 1982, 38: 3775

2c Ritter K. Synthesis 1993, 735 , particularly pages 756-7

For tosylate esters, see the following references.

3a With Ra/Ni: Kenner GW. Murray MA. J. Chem. Soc. 1949, S178

3b H₂NNH₂, Pd/CaCO₃: Rottendorf H. Sternhell S. Aust. J. Chem. 1963, 16: 647

3c Mesylate esters. With Pd/C: Clauss K. Jensen H. Angew. Chem., Int. Ed. Engl. 1973, 12: 918

3d Potassium aryl sulfates. With Ra/Ni: Lonsky W. Traitler H. Kratzl K. J. Chem. Soc., Perkin Trans. 1 1975, 169

3e Phenyl ethers. With Ra/Ni; also a few methyl ethers: Chandler GS. Sasse WHF. Aust. J. Chem. 1963, 16: 20

3f For 1-phenyl-5-tetrazolyl ethers, see the following references. With Pd/C: Musliner WJ. Gates JW. J. Am. Chem. Soc. 1966, 88: 4271

3g Musliner WJ. Gates JW. Org. Synth. 1971, 51: 82

3h

Catalytic transfer hydrogenation with H₂NNH₂·H₂O or NaH₂PO₂ or HCO₂H: Ref. 5b.

3i Phenyl urethanes. With Pd/C: Weaver JD. Eisenbraun EJ. Harris LE. Chem. Ind. (London) 1973, 187

3j O-Arylisoureas. With Pd/CaCO₃ or Pd/C: Vowinkel E. Wolff C. Chem. Ber. 1974, 107: 907

3k Nonaflates and other fluorosulfonates. With Pd/C: Subramanian LR. Martinez AG. Fernandez AH. Alvarez RM. Synthesis 1984, 481

For fluoroalkanesulfonates, see the following references.

4a With n-Bu₃NH⁺ HCO₂ ^-: Chen Q.-Y. He Y.-B. Yang Z.-Y. J. Chem. Soc., Chem. Commun. 1986, 1452

4b Et₃NH⁺ HCO₂ ^-: Chen Q.-Y. He Y.-B. Synthesis 1988, 896

4c For triflates see the following references. With Et₃NH⁺ HCO₂ ^-: Cacchi S. Ciattini PG. Morera E. Ortar G. Tetrahedron Lett. 1986, 27: 5541

4d

Et₃NH⁺ HCO₂ ^-: Ref. 1d.

4e

NaBH₄: Ref. 1e. For highly hindered, electron-rich phenols see the following references:

4f Saá JM. Dopico M. Martorell G. García-Raso A. J. Org. Chem. 1990, 55: 991

4g With Ni(0)/MeOH: Sasaki K. Sakai M. Sakakibara Y. Takagi K. Chem. Lett. 1991, 2017

4h Pd-catalyzed electrochemical reduction: Chiarotto I. Carelli I. Cacchi S. Pace P. J. Electroanal. Chem. 1995, 385: 235

4i Et₃SiH/Pd(OAc)₂, dppp or dppf: Kotsuki H. Datta PK. Hayakawa H. Suenaga H. Synthesis 1995, 1348

5a Phenyl ethers. With Na/NH₃: Sawa YK. Tsuji N. Maeda S. Tetrahedron 1961, 15: 144

5b Sawa YK. Tsuji N. Maeda S. Tetrahedron 1961, 15: 154

5c 2,4-Diaminophenyl ethers. With Na/NH₃: Pirkle WH. Zabriskie JL. J. Org. Chem. 1964, 29: 3124

5d For diethyl phosphate esters see the following references. With Li/NH₃; also a few mesylate esters: Kenner GW. Williams NR. J. Chem. Soc. 1955, 522

5e Li/NH₃: Pelletier SW. Locke DM. J. Org. Chem. 1958, 23: 131

5f Li/NH₃: Goldkamp AH. Hoehn WH. Mikulec RA. Nutting EF. Cook DL. J. Med. Chem. 1965, 8: 409

5g Li and Na/NH₃: Rossi RA. Bunnett JF. J. Org. Chem. 1973, 38: 2314

5h Li/NH₃: Dominianni SJ. Ryan CW. DeArmitt CW. J. Org. Chem. 1977, 42: 344

5i NaNaph and NaAnth: Shafer SJ. Closson WD. van Dijk JMF. Piepers O. Buck HM. J. Am. Chem. Soc. 1977, 99: 5118

5j

Ti(0)/THF: Ref. 2a.

5k Electrochemical reduction: Shono T. Matsumura Y. Tsubata K. Sugihara Y. J. Org. Chem. 1979, 44: 4508

6 Lusch MJ. Woller KR. Keller AM. Abstracts of Papers, 207th National Meeting of the American Chemical Society, San Diego, CA, March 13-18, 1994 American Chemical Society; Washington DC: 1994. ORGN 63.

7 Freeman PK. Hutchinson LL. J. Org. Chem. 1980, 45: 1924

8 Guijarro D. Mancheño B. Yus M. Tetrahedron 1994, 50: 8551

9a Curtis MD. Allred AL. J. Am. Chem. Soc. 1965, 87: 2554

9b Horne DA. J. Chem. Educ. 1983, 60: 246

10 The use of only 5 equivalents of CCl₄ in MeCN solvent may be more useful for phenols having limited solubility in non-polar CCl₄: Silverberg LJ. Dillon JL. Vemishetti P. Tetrahedron Lett. 1996, 37: 771

11a Stowell JK. Widlanski TS. Tetrahedron Lett. 1995, 36: 1825

11b Lusch MJ. Nodland MG. Abstracts of Papers, 211th National Meeting of the American Chemical Society, New Orleans, LA, March 24-28. 1996 American Chemical Society; Washington DC: 1996. ORGN 251.

12 Whitesides GM. Panek EJ. Stedronsky ER. J. Am. Chem. Soc. 1972, 94: 232

13 Still WC. Kahn M. Mitra A. J. Org. Chem. 1978, 43: 2923

14

Ar should be used rather than N₂ as the inert atmosphere because lithium reacts slowly with nitrogen to form lithium nitride, which coats the lithium surface and can slow the reaction with DTBB.