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Synlett 2007(13): 2101-2105  
DOI: 10.1055/s-2007-984543
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Novel Nickel(0)-Catalyzed Cascade Ullmann-Pinacol Coupling: From o-Bromobenzaldehyde to trans-9,10-Dihydroxy-9,10-dihydrophenanthrene

Shuang-zheng Lin, Qing-an Chen, Tian-pa You*
Department of Chemistry, University of Science and Technology of China, Hefei 230026, P. R. of China
e-Mail: ytp@ustc.edu.cn;
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Publication History

Received 9 April 2007
Publication Date:
27 June 2007 (online)

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Abstract

Using 5 mol% of (Ph3P)2NiCl2 as a catalyst, Zn powder as a reductant, ortho-carbonyl-substituted aryl halides could be ­coupled to form trans-9,10-dihydroxy-9,10-dihydrophenanthrenes in a one-pot cascade reaction.

Key words

Nickel catalysis - Ullmann-pinacol coupling - cascade reaction - trans-selectivity - trans-9,10-dihydroxy-9,10-dihydrophenanthrene

    References and Notes

  • 1a Seebach D. Beck AK. Heckel A. Angew. Chem. Int. Ed.  2001,  40:  93 
    CrossrefGoogle Scholar
  • 1b Blaser HU. Chem. Rev.  1992,  92:  935 
    CrossrefGoogle Scholar
  • 2 Chen Y. Yekta S. Yudin AK. Chem. Rev.  2003,  103:  3155 
    CrossrefPubMedGoogle Scholar
  • 3 For application of phendiol derivatives in asymmetric catalysis, Suzuki’s group has reported a valuable work recently. See: Ohmori K. Furuya S. Yamanoi S. Suzuki K. Chem. Lett.  2007,  36:  328 
    CrossrefGoogle Scholar
  • 4a Kitamura M. Ohmori K. Kawase T. Suzuki K. Angew. Chem. Int. Ed.  1999,  38:  1229 
    CrossrefGoogle Scholar
  • 4b Kelly TR. Li Q. Bhushan V. Tetrahedron Lett.  1990,  31:  161 
    CrossrefGoogle Scholar
  • 5a Cortex C. Harvey RG. Org. Synth., Coll. Vol. VI   Wiley and Sons; New York: 1988.  p.887 
    CrossrefGoogle Scholar
  • 5b Okajima M. Suga S. Itami K. Yoshida J. J. Am. Chem. Soc.  2005,  127:  6930 
    CrossrefGoogle Scholar
  • 6a Ohmori K. Kitamura M. Suzuki K. Angew. Chem. Int. Ed.  1999,  38:  1226 
    CrossrefGoogle Scholar
  • 6b Taniguchi N. Hata T. Uemura M. Angew. Chem. Int. Ed.  1999,  38:  1232 
    CrossrefGoogle Scholar
  • 6c Yamamoto Y. Hattori R. Itoh K. Chem. Commun.  1999,  825 
    CrossrefGoogle Scholar
  • 6d Yamamoto Y. Hattori R. Miwa T. Nakagai Y.-i. Kubota T. Yamamoto C. Okamoto Y. Itoh K. J. Org. Chem.  2001,  66:  3865 
    CrossrefGoogle Scholar
  • 6e Li C.-J. Meng Y. Yi X.-H. Ma J.-H. Chan T.-K. J. Org. Chem.  1998,  63:  7498 
    CrossrefGoogle Scholar
  • 7a Hassan J. Sévignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 
    CrossrefPubMedGoogle Scholar
  • 7b Bringmann G. Mortimer AJP. Keller PA. Gresser MJ. Garner J. Breuning M. Angew. Chem. Int. Ed.  2005,  44:  5384 
    CrossrefPubMedGoogle Scholar
  • 8a Chatterjee A. Joshi NN. Tetrahedron  2006,  62:  12137 
    CrossrefGoogle Scholar
  • 8b Tanaka K. Kishigami S. Toda F. J. Org. Chem.  1990,  55:  2981 
    CrossrefGoogle Scholar
  • 9a Scherf group reported a similar reaction to cis-phendiol with excess Ni(COD)2 in 1999: Reisch HA. Enkelmann V. Scherf U. J. Org. Chem.  1999,  64:  655 
    CrossrefGoogle Scholar
  • 9b

    The trans-structure of 2a was determined by the J 9,10 = 8.1 Hz and the singlet for acetate at δ = 2.11 ppm of trans-9-acetoxy-10-hydroxy-9,10-dihydrophenanthrene (Scheme [4] ).
    Crossref
  • 9c For cis-9-acetoxy-10-hydroxy-9,10-dihydrophenanthrene, J 9,10 = 3.8 Hz and the singlet for acetate is at δ = 1.92 ppm, see: Jerina DM. Selander H. Yagi H. Wells MC. Davey JF. Mahadevan V. Gilbson DT. J. Am. Chem. Soc.  1976,  98:  5988 
    CrossrefGoogle Scholar
  • 13 The phendiol 2a is stable in solid. But, in our observation, it could be oxidized to phenanthrenequinone in solution. The colorless solution of phendiol 2a changed to yellow in several hours, indicated that some phenanthrenequinone was formed. This conversion could be accelerated by silica gel or light, see: Barbas JT. Sigma ME. Dabestani R. Environ. Sci. Technol.  1996,  30:  1776 ; thus, the diol products must be separated as quickly as possible after ceasing the reaction to assure high yields
    CrossrefGoogle Scholar
  • Prepared from β-naphthol according to literature procedure:
  • 18a Russell A. Lockhart LB. Org. Synth., Coll. Vol. III   Wiley & Sons; New York: 1955.  p.463 
    Google Scholar
  • 18b Shoesmith JB. Mackie A. J. Chem. Soc.  1930,  1584 
    Google Scholar
  • Prepared from 2-methylnaphthalene according to literature procedure:
  • 19a Oi S. Matsunaga K.-i. Hattori T. Miyano S. Synthesis  1993,  895 
    CrossrefGoogle Scholar
  • 19b Smith JG. Dibble PW. Sandborn RE. J. Org. Chem.  1986,  51:  3762 
    CrossrefGoogle Scholar
  • 22 Sarobe M. van Heerbeek R. Jenneskens LW. Zwikker JW. Liebigs Ann./Recl.  1997,  2499 
    Google Scholar
  • 23 Prepared from 3,4,5-trimethoxybenzaldehyde according to literature procedure: Molander GA. George KM. Monovich LG. J. Org. Chem.  2003,  68:  9533 
    CrossrefGoogle Scholar
  • 24a Shi L. Fan C.-A. Tu Y.-Q. Wang M. Zhang F.-M. Tetrahedron  2004,  60:  2851 
    CrossrefGoogle Scholar
  • 24b Ogoshi S. Kamada H. Kurosawa H. Tetrahedron  2006,  62:  7583 
    CrossrefGoogle Scholar
10

The zinc powder was purchased from SCRC (Sinopharm Chemical Reagent Co., Ltd). The activation procedure was conducted as follows: The zinc powder was stirred in 1 M HCl for a few minutes to remove the oxide, then filtered and washed successively with H2O, EtOH, and Et2O. The material was dried in vacuum for 24 h and then stored in a sealed bottle.

11

Synthesis of (Ph 3 P) 2 NiCl 2 from NiCl 2 ·6H 2 O and PPh 3 Nickel(II) chloride hexahydrate and PPh3 were purchased from SCRC and used as available. Then, PPh3 (10.50 g, 40 mmol) was dissolved in 100 mL of warm AcOH, and then cooled to r.t. To this solution, NiCl2·6H2O (4.76 g, 20 mmol) in H2O (4 mL) was added dropwise. The mixture was stirred at r.t. for 48 h. The dark green solution was filtered, yielding deep green solid, which was washed successively with AcOH, EtOH, and Et2O. The material was dried in vacuum for 24 h and then stored in a sealed bottle.

12

Addition of PPh3 seems to accelerate the Ullmann coupling step. When 28 mol% of PPh3 was added and the reaction was ceased in 53 min, the biphenyl-2,2′-dialdehyde can be isolated with 80% yield. But the second step of pinacol coupling was not affected by PPh3.

14

In solution, 2b and 2c were oxidized faster than 2a in our observation. That resulted in lower yield of 2b and 2c.

15

The coordination of the Zn2+ with both the carbonyls, which brings the two carbonyls together, is essential to the intramolecular pinacol coupling. In the reaction of heterocyclic 1h, this effect may be disturbed by the competitive coordination of the nitrogen atom on the heterocycle.

16

Typical Procedure for the (Ph 3 P) 2 NiCl 2 -Catalyzed Ullmann-Pinacol Coupling To a mixture of (Ph3P)2NiCl2 (33 mg, 0.05 mmol) and zinc powder (196 mg, 3 mmol) in anhyd DMF (0.5 ml) was added the 2-bromobenzaldehyde (1a, 185 mg, 117 µL, 1 mmol) at 60 °C under a nitrogen atmosphere. This mixture was stirred for 7 h. After cooling to ambient temperature, 5 mL 1 M HCl and 10 mL CH2Cl2 were added. The mixture was stirred for 10 min, and then filtered to remove the unreacted zinc powder. The phases were separated and the aqueous phase was extracted with CH2Cl2 (3 × 5 mL). The combined organic extracts were dried over MgSO4 for 1 h and concentrated. Purification of the residue by chromatography gave the phendiol 2a (85 mg, 80% yield).

17

Selective NMR Data of Products Compound 2a: 1H NMR (300 MHz, CDCl3): δ = 7.76 (dd, J = 6.2, 2.8 Hz, 2 H), 7.67 (dd, J = 9.4, 3.1 Hz, 2 H), 7.42-7.36 (m, 4 H), 4.76 (s, 2 H), 1.65 (br, 2 H). 13C NMR (75 MHz, CDCl3): δ = 136.2, 132.6, 128.6, 128.5, 125.3, 123.9, 74.2.
Compound 2b: 1H NMR (300 MHz, acetone-d 6): δ = 8.41 (d, J = 8.4 Hz, 2 H), 8.21 (d, J = 8.7 Hz, 2 H), 8.02 (d, J = 8.7 Hz, 2 H), 7.95 (d, J = 7.8 Hz, 2 H), 7.64-7.51 (m, 4 H), 5.69 (s, 2 H), 3.13 (s, 2 H). 13C NMR (75 MHz, acetone-d 6): δ = 134.3, 133.9, 132.1, 131.5, 129.8, 129.2, 127.5, 126.6, 124.8, 123.5, 67.9.
Compound 2c: 1H NMR (300 MHz, CDCl3): δ = 8.00 (d, J = 8.4 Hz, 2 H), 7.95-7.91 (m, 4 H), 7.56 (d, J = 8.4 Hz, 2 H), 7.46 (t, J = 7.5 Hz, 2 H), 7.27 (t, J = 6.6 Hz, 2 H), 4.73 (s, 2 H), 2.61 (br, 2 H). 13C NMR (75 MHz, CDCl3): δ = 136.2, 133.8, 130.2, 129.1, 129.1, 128.5, 127.6, 125.6, 125.4, 121.4, 75.0.
(18) Compound 2e: 1H NMR (300 MHz, acetone-d 6): δ = 7.78-7.72 (m, 4 H), 7.34-7.29 (m, 4 H), 3.04 (s, 2 H), 1.24 (s, 6 H). 13C NMR (75 MHz, acetone-d 6): δ = 144.8, 132.7, 128.8, 128.0, 125.1, 124.0, 77.3, 25.0.
Compound 2f: 1H NMR (300 MHz, acetone-d 6): δ = 7.71 (dd, J = 8.4, 6.0 Hz, 2 H), 7.60 (dd, J = 10.3, 2.5 Hz, 2 H), 7.13 (td, J = 8.6, 2.5 Hz, 2 H), 4.60 (s, 2 H), 3.12 (s, 2 H). 13C NMR (75 MHz, acetone-d 6): δ = 163.7 (d, J = 241.0 Hz), 135.1 (d, J = 2.9 Hz), 134.7 (dd, J = 8.0, 2.3 Hz), 129.0 (d, J = 8.4 Hz), 115.6 (d, J = 21.5 Hz), 111.2 (d, J = 23.1 Hz), 73.416.
Compound 4: 1H NMR (300 MHz, CDCl3): δ = 8.48 (s, 4 H), 7.55 (d, J = 4.5 Hz, 2 H), 4.81 (s, 4 H), 2.96 (br, 2 H). 13C NMR (75 MHz, CDCl3): δ = 148.7, 148.1, 147.8, 129.8, 122.08, 61.28.

20

Compound 1d was prepared from 9-bromophenanthrene in five steps (Scheme [5] ).

21

Pure diol product was not obtained. The most polar product was supposed to be the mixture of cis-diol and trans-diol by NMR analysis.

25

Preparation in multigram scale is feasible, the dosage of nickel catalyst can be reduced to 0.03 equiv: To a mixture of (Ph3P)2NiCl2 (392 mg, 0.60 mmol) and zinc powder (3.930 g, 60.1 mmol) in anhyd DMF (10 mL) was added the 2-bromobenzaldehyde (1a, 3.70 g, 2.34 mL, 20 mmol) at 60 °C under nitrogen atmosphere. After stirring for 7 h, the mixture was poured into ice water (50 mL) and filtered. The filtrate was discarded. The filter residue was dissolved in hot EtOAc and filtered again. Concentration of the filtrate gave crude phendiol 2a, which is easily recrystallized in EtOAc or EtOH to afford pure product (1.683 g, 79% yield).

26

The trans-structures of the phendiols in Table [1] were confirmed based on NMR analysis of the diols and the corresponding monoacetates (see ref. 9).
Typical Procedure for Phendiol Monoacetate Method A (2a, 2c, 2f): To a suspension of phendiol (0.05 mmol) and Na2CO3 (16 mg, 0.15 mmol) in anhyd EtOAc (0.5 mL), Ac2O (15 mg, 14 µL, 0.15 mmol) was added at r.t. After the reaction was complete (monitored by TLC), the mixture was poured into 2 mL of cold H2O and the phases were separated. The aqueous phase was extracted with EtOAc (3 × 1 mL). The combined organic extracts were concentrated. Purification of the residue by chromatography gave the monoacetate.
Method B (2b): To a solution of 2b (18 mg, 0.058 mmol) in 0.5 mL pyridine, Ac2O (8.9 mg, 8.2 µL, 0.087 mmol) was added at r.t. The reaction was conducted for 10 h. Conventional procedures led to the isolation of the monoacetate (5 mg, 24.5%).
Selective NMR Data of Phendiol Monoacetates Monoacetate of 2a: 1H NMR (300 MHz, CDCl3): δ = 7.75 (m, 2 H), 7.55 (d, J = 7.2 Hz, 1 H), 7.41-7.22 (m, 5 H), 6.02 (d, J = 8.1 Hz, 1 H), 4.82 (d, J = 8.1 Hz, 1 H), 2.48 (s, 1 H), 2.11 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 171.3, 135.5, 133.1, 132.3, 132.0, 129.2, 128.9, 128.5, 128.1, 127.6, 127.1, 123.9, 123.8, 74.5, 71.1, 21.1.
Monoacetate of 2b: 1H NMR (300 MHz, acetone-d 6): δ = 8.38 (d, J = 8.4 Hz, 1 H), 8.28-8.25 (m, 3 H), 8.13-8.06 (m, 2 H), 8.00-7.96 (m, 2 H), 7.67-7.53 (m, 4 H), 7.06 (d, J = 2.4 Hz, 1 H), 5.66 (d, J = 2.4 Hz, 1 H), 3.07 (br, 1 H), 1.84 (s, 3 H). 13C NMR (75 MHz, acetone-d 6): δ = 171.0, 134.5, 134.3, 133.6, 133.5, 133.4, 131.4, 131.3, 131.1, 130.3, 129.5, 129.3, 128.2, 127.8, 127.2, 126.9, 124.7, 124.0, 123.5, 123.4, 68.7, 65.1, 20.9.
Monoacetate of 2c: 1H NMR (300 MHz, CDCl3): δ = 8.00-7.90 (m, 5 H), 7.57-7.43 (m, 5 H), 7.29-7.24 (m, 2 H), 6.06 (d, J = 11.1 Hz, 1 H), 4.92 (d, J = 11.1 Hz, 1 H), 2.65 (br, 1 H), 2.38 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 172.0, 136.1, 133.9, 133.8, 132.8, 130.2, 130.0, 129.3, 129.0, 128.8, 128.44, 128.39, 127.6, 127.5, 125.8, 125.7, 126.5, 125.4, 121.6, 121.0, 76.6, 73.4, 21.1.
Monoacetate of 2f: 1H NMR (300 MHz, acetone-d 6): δ = 7.73-7.63 (m, 3 H), 7.45 (dd, J = 8.4, 5.7 Hz, 1 H), 7.19-7.07 (m, 2 H), 5.96 (d, J = 7.2 Hz, 1 H), 4.84 (d, J = 7.2 Hz, 1 H), 3.03 (s, 1 H), 2.09 (s, 3 H). 13C NMR (75 MHz, acetone-d 6): δ = 170.9, 165.8 (d, J = 17.1 Hz), 162.6 (d, J = 16.2 Hz), 135.8 (dd, J = 8.2, 2.4 Hz), 134.7 (dd, J = 8.0, 2.2 Hz), 133.6 (d, J = 2.9 Hz), 131.3 (d, J = 8.6 Hz), 130.9 (d, J = 8.5 Hz), 130.0 (d, J = 3.0 Hz), 116.2 (d, J = 14.3 Hz), 115.8 (d, J = 14.5 Hz), 112.0 (d, J = 15.9 Hz), 111.6 (d, J = 15.9 Hz), 74.2, 70.1, 21.0.