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

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.

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

References and Notes

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See also:

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Richmond et al. reported that the chelation-assisted oxidative addition of Ar-X to W(CO)₃(EtCN)₃ proceeded smoothly to give air-stable, seven-coordinate tungsten(II) complexes. However, this reaction was limited to specific aryl halides bearing a bidentate or tridentate chelating group and was not applied to synthetic reactions, see:

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15 Larhed et al. reported the palladium-catalyzed carbonylation of aryl halides using Mo(CO)₆ as a carbonyl source, see: Wu X. Ekegren JK. Larhed M. Organometallics  2006,  25:  1434 ; and references cited therein, see also ref 12b

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.

19 For an example of a related mechanism, see: Qian H. Pei T. Widenhoefer RA. Organometallics  2005,  24:  287 ; see also ref 12a

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.