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Synlett 2007(6): 0929-0933  
DOI: 10.1055/s-2007-973858
LETTER
© Georg Thieme Verlag Stuttgart · New York

Intermolecular Addition Reaction to Alkenes of Acylmolybdenum Complexes Generated by Oxidative Addition of Aryl or Alkenyl Halides with Molybdenum(0) Carbonyl Complexes

Kenichiro Sangu, Toru Watanabe, Jun Takaya, Nobuharu Iwasawa*
Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan
Fax: +81(3)57342931; e-Mail: niwasawa@chem.titech.ac.jp;
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Publication History

Received 18 January 2007
Publication Date:
26 March 2007 (online)

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Abstract

Acylmolybdenum species, generated by oxidative addition of aryl or alkenyl halides with molybdenum(0) carbonyl complex followed by carbon monoxide insertion, added to various kinds of alkenes intermolecularly to give simple addition products in good yields without formation of carbonylative Heck-type products.

Key words

molybdenum hexacarbonyl - acylmolybdenum - oxidative addition of aryl or alkenyl halides

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16

The use of other solvents such as THF, 1,4-dioxane, toluene and dibutyl ether at reflux temperature resulted in low conversion.

17

Typical Procedure: A mixture of aryl iodide 1m (51 mg, 0.20 mmol), Mo(CO)6 (53 mg, 0.20 mmol) and ethyl acrylate (2a, 0.22 mL, 2.0 mmol) was heated in DMF at 160 °C for 1 h under an Ar atmosphere. After complete consumption of the aryl iodide 1m was confirmed by TLC, the reaction was quenched at r.t. with phosphate buffer (pH 7). The product was extracted with Et2O (4 ×) and the combined organic extracts were washed with brine and dried over MgSO4. The solvent was removed under reduced pressure and the residue was purified by preparative TLC (silica gel, hexane-EtOAc, 5:1) to afford product 3m (40 mg, 78%).
Spectral Data for Selected Compounds
Ethyl 4-(naphthalen-1-yl)-4-oxobutanoate (3m)
1H NMR (300 MHz, CDCl3): δ = 1.28 (t, J = 7.1 Hz, 3 H), 2.83 (t, J = 6.6 Hz, 2 H), 3.37 (t, J = 6.6 Hz, 2 H), 4.19 (q, J = 7.1 Hz, 2 H), 7.45-7.65 (m, 3 H), 7.87 (d, J = 7.7 Hz, 1 H), 7.94 (d, J = 7.3 Hz, 1 H), 7.99 (d, J = 8.4 Hz, 1 H), 8.60 (d, J = 8.6 Hz, 1 H); 13C NMR (75 MHz, CDCl3): δ = 14.15, 28.65, 36.64, 60.65, 124.31, 125.73, 126.39, 127.48, 127.85, 128.31, 130.03, 132.61, 133.87, 135.61, 172.80, 202.25; IR (KBr): 2981, 1732, 1684 cm-1; Anal Calcd for C16H16O3: C, 74.98; H, 6.29. Found: C, 74.69; H, 6.39.
1-(Naphthalen-1-yl)-3-(4-methoxyphenyl)propan-1-one (5h) 1H NMR (300 MHz, CDCl3): δ = 3.09 (t, J = 7.7 Hz, 2 H), 3.36 (t, J = 7.7 Hz, 2 H), 3.79 (s, 3 H), 6.84 (d, J = 8.7 Hz, 2 H), 7.18 (d, J = 8.7 Hz, 2 H), 7.43-7.66 (m, 3 H), 7.81 (d, J = 7.3 Hz, 1 H), 7.87 (d, J = 7.8 Hz, 1 H), 7.98 (d, J = 8.3 Hz, 1 H), 8.54 (d, J = 8.5 Hz, 1 H); 13C NMR (75 MHz, CDCl3): δ = 29.74, 44.10, 55.25, 113.93, 124.33, 125.76, 126.41, 127.31, 127.82, 128.36, 129.36, 130.10, 132.48, 133.11, 133.93, 136.08, 158.00, 203.72; ΙR (KBr): 3048, 1681, 1247 cm-1; Anal Calcd for C20H18O2: C, 82.73; H, 6.25. Found: C, 82.49; H, 6.42.
2-Ethyl-1-indanone (11b) 1H NMR (300 MHz, CDCl3): δ = 1.01 (t, J = 7.5 Hz, 3 H), 1.49-1.60 (m, 1 H), 1.90-2.05 (m, 1 H), 2.55-2.66 (m, 1 H), 2.82 (dd, J = 3.8, 17.4 Hz, 1 H), 3.32 (dd, J = 7.9, 17.4 Hz, 1 H), 7.36 (t, J = 7.6 Hz, 1 H), 7.46 (d, J = 7.6 Hz, 1 H), 7.58 (t, J = 7.6 Hz, 1 H), 7.75 (d, J = 7.6 Hz, 1 H); 13C NMR (75 MHz, CDCl3): δ = 11.60, 24.46, 32.32, 48.75, 123.83, 126.53, 127.28, 134.60, 136.96, 153.82, 208.97; IR (KBr): 2961, 1709 cm-1; Anal Calcd for C11H12O: C, 82.46; H, 7.55. Found: C, 82.70; H, 7.54.

18

3m and 5g were obtained in lower yield in the absence of CO.

20

No H-D exchange was observed when partially deuterated ketone 5g was heated in DMF at 160 °C.

21

We tried the reaction using D2O for the quenching but no deuterium incorporation in the product was observed. Thus, at present, we believe that the molybdenum enolate intermediate is protonated during the reaction by the small amount of water present in DMF.

22

Palladium-catalyzed intramolecular carbonylative cyclization was limited to terminal olefins in the case of indanone synthesis, see ref 12.