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

1a Diederich F. Stang PJ. Metal-Catalyzed Cross-Coupling Reactions   VCH; Weinheim: 1998. 

1b Tsuji J. Palladium Reagents and Catalysis   Wiley and Sons; Chichester: 1995. 

2 Stille JK. Angew. Chem., Int. Ed. Engl.  1986,  25:  508 

For reviews, see:

3a Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 

3b Suzuki A. Metal-Catalyzed Cross-Coupling Reaction   Diederich F. Stang PJ. VCH; Weinheim: 1998.  p.48 

4 Negishi E. Organozinc Reactions   Knochel P. Jones P. Oxford University Press; Oxford, UK: 1999.  Chap. 11.

5 Kumada M. Pure Appl. Chem.  1980,  52:  669 

6a Gotov B. Kaufmann J. Schumann H. Schmalz H.-G. Synlett  2002,  361 

6b Gotov B. Kaufmann J. Schumann H. Schmalz H.-G. Synlett  2002,  1 

6c Blum J. Katz JA. Jaber N. Michmann M. Schumann H. Schutte S. Kaufmann J. Wassermann BC. J. Mol. Catal. A: Chem.  2001,  165:  97 

6d Baidossi W. Blum J. Frick M. Gelmann D. Heymer B. Schumann H. Schutte S. Shakh E. Organic Synthesis via Organometallics, OSM 5   Helmchen G. Dibo J. Flubach D. Vieweg & Sohn; Braunschweig: 1997.  p.51 

6e Blum J. Berlin O. Milstein D. Ben-David Y. Wassermann BC. Schutte S. Schumann H. Synthesis  2000,  571 

6f Gelmann D. Schumann H. Blum J. Tetrahedron Lett.  2000,  41:  7555 

6g Blum J. Gelmann D. Baidossi W. Shakh E. Rosenfeld A. Aizenshtat Z. Wassermann BC. Frick M. Heymer B. Schutte S. Wernik S. Schumann H. J. Org. Chem.  1997,  62:  8681 

6h Gelman D. Dechert S. Schumann H. Blum J. Inorg. Chim. Acta  2002,  334:  14 

6i Blum J. Gelmann D. Aizenshtat Z. Wernik S. Schumann H. Tetrahedron Lett.  1998,  39:  5611 

6j Schumann H. Kaufmann J. Wassermann BC. Girgdies F. Jaber N. Blum J. Z. Anorg. Allg. Chem.  2002,  628:  971 

7 Schumann H. Kaufmann J. Dechert S. Schmalz H.-G. Velder J. Tetrahedron Lett.  2001,  42:  5405 

8 Schumann H. Kaufmann J. Dechert S. Schmalz H.-G. Tetrahedron Lett.  2002,  43:  3507 

9

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).

10 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:

11a Semmelhack MF. Seufert W. Keller L. J. Am. Chem. Soc.  1980,  102:  6584 

11b Davies SG. Furtado OMLR. Hepworth D. Loveridge T. Synlett  1995,  69 

11c Gibson SE. Gil R. Prechtl F. White AJP. Williams DJ. J. Chem. Soc., Perkin Trans. 1  1996,  1007 

11d Dehmel F. Schmalz H.-G. Org. Lett.  2001,  3:  3579 

11e Dehmel F. Lex J. Schmalz H.-G. Org. Lett.  2002,  4:  3915 

12

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.

13

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).

14

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:

15a Carpentier J.-F. Petit F. Mortreux A. Dufaud V. Basset J.-M. Thivolle-Cazat J. J. Mol. Catal.  1993,  81:  1 

15b For some recent work, see: Müller TJJ. Ansorge M. Aktah D. Angew. Chem.  2000,  112:  1323 

15c Crousse B. Xu L.-H. Bernardinelli G. Kündig EP. Synlett  1998,  658 

15d Bräse S. Tetrahedron Lett.  1999,  40:  6757 

16

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.

17

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.

18

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).

19

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.

20

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.

21 Uemura M. Nishimura H. Hayashi T. J. Organomet. Chem.  1994,  473:  129