Pd-Catalyzed Cross-Coupling of Haloarenes and Chloroarene-Cr(CO)₃ Complexes with Stabilized Vinyl- and Allylaluminium Reagents

Abstract

The palladium-catalyzed cross-coupling of intramolecularly stabilized divinyl- and diallylaluminium compounds 1 and 2 with haloarenes and chloroarene-Cr(CO)₃ complexes has been studied. The coupling products were obtained in high yields (up to 98%) under relatively mild conditions (40-60 °C in THF, 3-12 h) in the presence of 5-10 mol% of PdCl₂(PPh₃)₂.

allyl complexes - aluminium reagents - arene complexes - cross-coupling - palladium - vinyl complexes

References

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<A NAME="RG13303ST-9">9</A>

Typical experimental procedure: The vinylaluminium reagent 1 (0.21 mg, 1.25 mmol), PdCl₂(PPh₃)₂ (5 mol%, 0.06 mmol), and 2-bromonaphthalene(3) (0.26 g, 1.25 mmol) were placed in a flame dried Schlenk-flask equipped with a reflux condenser, evacuated and flushed with N₂. Deoxygenated anhyd THF (20 mL) was added via syringe. The reaction mixture was stirred at 60 °C for 12 h under a N₂ atmosphere, cooled to ambient temperature, diluted with n-hexane (20 mL), filtered trough a short pad of silica gel, washed with hexane and concentrated under reduced pressure. The residue was purified by chromatography on silica gel (20 g) with n-hexane-ethyl acetate = 10:1 to give the product 4 as (0.19 g, 1.23 mmol, 98%) a colorless oil. ¹H NMR (CDCl₃, 200 MHz): δ = 8.27-8.32 (m, 1 H, H _aryl), 7.93-8.04 (m, 2 H, H _aryl), 7.80 (m, 1 H, H _aryl), 7.57-7.72
(m, 4 H, H _aryl, -CH=CH₂), 5.97 (dd, 1 H, J = 1.58, 17.3 Hz,
-CH=CHH _trans ), 5.65 (dd, 1 H, J = 1.58, 10.9 Hz,
-CH=CH _cis H). ¹³C NMR (CDCl₃, 50 MHz): δ = 135.5, 134.3 (C _q), 133.6 (-CH=CH₂), 131.1 (C _q), 128.5, 128.1, 126.0, 125.7, 125.6, 123.7, 123.6 (C _aryl), 116.97 (-CH=CH₂).

<A NAME="RG13303ST-10">10</A> See for instance: Wilhelm R. Widdowson DA. J. Chem. Soc., Perkin Trans. 1  2000,  3808 

For typical reactions and synthetic applications of styrene Cr(CO)₃ derivatives, see:

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<A NAME="RG13303ST-11B">11b</A> Davies SG. Furtado OMLR. Hepworth D. Loveridge T. Synlett  1995,  69 

<A NAME="RG13303ST-11C">11c</A> Gibson SE. Gil R. Prechtl F. White AJP. Williams DJ. J. Chem. Soc., Perkin Trans. 1  1996,  1007 

<A NAME="RG13303ST-11D">11d</A> Dehmel F. Schmalz H.-G. Org. Lett.  2001,  3:  3579 

<A NAME="RG13303ST-11E">11e</A> Dehmel F. Lex J. Schmalz H.-G. Org. Lett.  2002,  4:  3915 

<A NAME="RG13303ST-12">12</A>

Typical experimental procedure: η ⁶ -(Vinylbenzene)-tricarbonylchromium(0) ( 28). η⁶-(Chlorobenzene)tricar-bonylchromium(0)(23) (124.3 mg, 0.5 mmol), vinylalane 1 (84.6 mg, 0.5 mmol) and PdCl₂(PPh₃)₂ (17.6 mg, 0.025 mmol) were placed under Ar in a flame dried Schlenk flask equipped with a reflux condenser. Deoxygenated anhydrous THF (5.0 mL) was added via a syringe and the reaction mixture was degassed three times. After stirring at 40 °C for 3 h the reaction mixture was cooled in an ice-bath, diluted with n-hexane (5 mL), filtered through a short column of silica gel (30 × 50 mm), eluted with n-hexane-MTBE = 8:1 (40 mL) and finally with n-hexane-MTBE = 4:1 (40 mL). Upon concentration of the filtrate the obtained orange-yellowish solid was recrystallized from MTBE-n-hexane to afford 28 (114.3 mg, 0.476 mmol, 95.2%) as yellow-orange crystals.

<A NAME="RG13303ST-13">13</A>

η ⁶ -(Vinylbenzene)tricarbonylchromium(0) ( 28). ¹H NMR (C₆D₆, 250 MHz): δ = 5.69 (dd, 1 H, J = 10.9, 17.5 Hz, -CH=CH₂), 5.11 (d, 1 H, J = 17.5 Hz, -CH=CHH _trans ), 4.85 (d, 1 H, J = 10.9 Hz, -CH=CH _cis H), 4.53 (ψd, 2 H, H _aryl), 4.43 (ψt, 2 H, H _aryl), 4.30 (m, 1 H, H _aryl). ¹³C NMR (C₆D₆,
63 MHz): δ = 233.2 (CO), 133.7 (-CH=CH₂), 115.8
(-CH=CH₂), 105.3 (C _q), 92.5, 90.9, 90.3 (C _aryl). Mp 80 °C (lit. [21] 79-80 °C).

<A NAME="RG13303ST-14">14</A>

η ⁶ -(4-Methyl-1-vinylbenzene)tricarbonylchromium(0) ( 29). ¹H NMR (C₆D₆, 250 MHz): δ = 5.73 (dd, 1 H, J = 10.9, 17.5 Hz, -CH=CH₂), 5.16 (d, 1 H, J = 17.5 Hz,
-C=CHH _trans ), 4.84 (d, 1 H, J = 10.9 Hz, -CH=CH _cis H), 4.77 (d, 2 H, J = 6.3 Hz, H _aryl), 4.36 (d, 2 H, J = 6.3 Hz). ¹³C NMR (C₆D₆, 63 MHz): δ = 233.5 (CO), 133.4 (-CH=CH₂), 114.9 (-CH=CH₂), 108.0, 102.7 (C _q), 92.5, 91.9 (C _aryl), 19.9 (Ar-CH₃). Mp 80 °C.

For a review about C_Ar-Cl bond activation through Cr(CO)₃ complexation, see:

<A NAME="RG13303ST-15A">15a</A> Carpentier J.-F. Petit F. Mortreux A. Dufaud V. Basset J.-M. Thivolle-Cazat J. J. Mol. Catal.  1993,  81:  1 

<A NAME="RG13303ST-15B">15b</A> For some recent work, see: Müller TJJ. Ansorge M. Aktah D. Angew. Chem.  2000,  112:  1323 

<A NAME="RG13303ST-15C">15c</A> Crousse B. Xu L.-H. Bernardinelli G. Kündig EP. Synlett  1998,  658 

<A NAME="RG13303ST-15D">15d</A> Bräse S. Tetrahedron Lett.  1999,  40:  6757 

<A NAME="RG13303ST-16">16</A>

η ⁶ -(1-Chloro-2-vinylbenzene)tricarbonylchromium(0) ( 30). ¹H NMR (CDCl₃, 250 MHz): δ = 6.75 (dd, 1 H, J = 10.9, 17.4 Hz, -CH=CH₂), 5.72 (d, 1 H, J = 17.4 Hz,
-C=CHH _trans ), 5.72 (dd, 1 H, H _aryl), 5.49 (dd, 1 H, H _aryl), 5.43 (d, 1 H, J = 10.9 Hz, -CH=CH _cis H), 5.39-5.34 (m, 1 H, H _aryl), 5.16-5.10 (m, 1 H, H _aryl). ¹³C NMR (CDCl₃, 63 MHz): δ = 231.5 (CO), 130.5 (-CH=CH₂), 117.9 (-CH=CH₂), 102.6 (C _q), 91.8, 91.6 (C _aryl), 90.2 (C _q), 89.4, 88.8 (C _aryl). Mp 73 °C.

<A NAME="RG13303ST-17">17</A>

η ⁶ -(1,2-Divinylbenzene)tricarbonylchromium(0) ( 31). ¹H NMR (CDCl₃, 250 MHz) δ = 6.62 (dd, 2 H, J = 10.9, 17.3 Hz, -CH=CH₂), 5.64 (d, 2 H, J = 17.3 Hz, -CH=CHH _trans ), 5.54-5.49 (m, 2 H, H _aryl), 5.41 (d, 2 H, J = 10.9 Hz,
-CH=CH _cis H), 5.37-5.34 (m, 2 H, H _aryl). ¹³C NMR (CDCl₃, 63 MHz) δ = 232.8 (CO), 131.7 (-CH=CH₂), 188.8
(-CH=CH₂), 105.1 (C _q), 91.6, 90.2 (C _aryl). Mp 85 °C.

<A NAME="RG13303ST-18">18</A>

η ⁶ -(1-Chloro-2-methyl-3-vinylbenzene)tricarbonyl-chromium(0) ( 32). ¹H NMR (C₆D₆, 300 MHz) δ = 6.12 (dd, 1 H, J = 11.0, 17.2 Hz, -CH=CH₂), 5.07 (d, 1 H, J = 17.2,
-CH=CHH _trans ), 4.92 (d, 1 H, J = 11.0 Hz, -CH=CH _cis H), 4.81 (m, 1 H, H _aryl ), 4.50 (m, 1 H, H _aryl ), 4.34 (m, 1 H, H _aryl ), 1.84 (s, 1 H, Ar-CH ₃ ). ¹³C NMR (C₆D₆, 75 MHz) δ = 232.5 (CO), 132.2 (-CH=CH₂), 119.0 (-CH=CH₂), 112.7, 106.0, 104.1 (C _q ), 91.9, 90.5, 88.1 (C _q ), 1.84 (Ar-CH₃). (Shifts were taken from crude product NMR).

<A NAME="RG13303ST-19">19</A>

η ⁶ -(1-Methyl-2,6-divinylbenzene)tricarbonyl-chromium(0) ( 33). ¹H NMR (C₆D₆, 250 MHz) δ = 6.20 (dd, 2 H, J = 10.9, 17.1 Hz, -CH=CH₂), 5.16 (d, 2 H, J = 17.1 Hz, -CH=CHH _trans ), 4.96-4.91 (m, 4 H, H _aryl, -CH=CH _cis H), 4.51 (t, 1 H, J = 6.6 Hz), 1.70 (s, 3 H, Ar-CH ₃). ¹³C NMR (C₆D₆, 63 MHz) δ = 233.6 (CO), 132.8 (-CH=CH₂), 118.1 (-CH=CH₂), 105.7, 105.5 (C _q), 91.1, 90.0 (C _aryl), 14.8 (Ar-CH₃). Mp 85 °C.

<A NAME="RG13303ST-20">20</A>

η ⁶ -(2-Methyl-3-vinyl-methylbenzoate)tricarbonyl-chromium(0) ( 34) ¹H NMR (C₆D₆, 250 MHz) δ = 6.10 (dd, 1 H, J = 10.7, 17.1 Hz, -CH=CH₂), 5.62 (dd, 1 H, J = 1.2, 6.6 Hz, H _aryl), 5.11 (dd, 1 H, J = 0.8, 17.1 Hz, -CH=CHH _trans ), 5.05 (dd_br, 1 H, J = 1.2, 6.6 Hz, H _aryl), 4.87 (dd, 1 H, J = 0.7, 10.7 Hz, -CH=CH _cis H), 4.27 (ψt, 1 H, J = 6.6 Hz, H _aryl), 3.30 (s, 3 H, OCH ₃), 2.29 (s, 3 H, Ar-CH ₃). ¹³C NMR (C₆D₆, 63 MHz) δ = 231.8 (CO), 166.4 (CO₂CH₃), 132.3 (-CH=CH₂), 118.4 (-CH=CH₂), 109.0, 104.6 (C _q), 95.8, 93.7 (C _aryl), 92.0 (C _q), 87.3 (C _aryl), 52.1 (OCH₃), 16.3 (Ar-CH₃). Mp 50 °C.

<A NAME="RG13303ST-21">21</A> Uemura M. Nishimura H. Hayashi T. J. Organomet. Chem.  1994,  473:  129