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Synlett 2009(11): 1800-1802  
DOI: 10.1055/s-0029-1217327
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Stille Cross-Coupling Reactions Using Vinylcyclopropylstannanes

Gerald Pattenden*, Davey A. Stoker
School of Chemistry, The University of Nottingham, Nottingham, NG7 2RD, UK
Fax: +44(115)9513535; e-Mail: gp@nottingham.ac.uk;
Further Information

Publication History

Received 3 February 2009
Publication Date:
02 June 2009 (online)

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Abstract

The Stille cross-coupling reaction between a vinylcyclopropylstannane and iodobenzene or phenol triflate provides an expedious route to 1,2-phenylvinylcyclopropanes. However, similar coupling reactions using ortho-substituted aromatic substrates also lead to butylaromatic products, resulting from competitive sp³-sp² coupling reactions.

Key words

Stille reaction - cross-coupling - arylations - vinyl cyclopropanes - sp³-sp² coupling

    References and Notes

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6

The vinylcyclopropylstannane 3 was obtained as a colourless oil. IR (CHCl3): νmax = 3083, 1631 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 0.11 (1 H, ddd, J = 10.5, 8.5, 5.5 Hz, CHSnBu3), 0.70-0.76 (2 H, m, CHCH 2CH), 0.81 (6 H, t, J = 8.0 Hz, SnCH2), 0.89 (9 H, t, J = 7.5 Hz, CH2CH 3), 1.25-1.36 (6 H, m, CH3CH 2), 1.36-1.44 (1 H, m, CH2=CHCH), 1.44-1.56 (6 H, m, SnCH2CH 2), 4.80 (1 H, dd, J = 10.0, 1.5 Hz, HHC=CH), 5.05 (1 H, dd, J = 17.0, 1.5 Hz, HHC=CH), 5.29 (1 H, ddd, J = 17.0, 10.0, 9.0 Hz, CH2=CH) ppm. ¹³C NMR (100 MHz, CDCl3): δ = 2.6 (CH), 8.7 (CH2), 11.5 (CH2), 13.7 (CH3), 19.4 (CH), 27.3 (CH2), 29.1 (CH2), 110.5 (CH2), 144.6 (CH) ppm. MS (EI): m/z C13H25Sn [M + - Bu]: 301.0978; 301.0986.

7

Typical Stille Coupling Procedure: Pd(OAc)2 (10 mol%), Ph3As (60 mol%), CuI (20 mol%), and LiCl (6 equiv) were dissolved in NMP, and the mixture was then stirred at r.t. under an argon atmosphere for 10 min. A soln of the aryltriflate or aryliodide (1.0 equiv.) and the stannane 3 (1.05 equiv) in NMP was added dropwise over 1 min, and the mixture was then degassed and heated to 80 ˚C for 24 h. The cooled mixture was poured onto H2O (50 mL) and EtOAc (50 mL), and the separated aqueous extract was extracted with EtOAc (3 × 100 mL). The combined organic extracts were washed successively with H2O (3 × 20 mL), 2 M aq HCl (10 mL) and brine (50 mL), then dried (Na2SO4) and concentrated in vacuo to leave the coupled product (s) as a colourless oil. Chromatographic separation and purification was carried out on SiO2, using PE (bp 40-60 ˚C), then 1-6% EtOAc in PE as eluant. The o-butylphenol (10a) showed identical spectroscopic data to those reported in the literature.¹0
Butylcinnamate 10b
IR (CHCl3): νmax = 1727cm-¹. ¹H NMR (360 MHz, CDCl3): δ = 0.94 (3 H, t, J = 7.0 Hz, CH2CH 3), 1.35 (3 H, t, J = 7.0 Hz, OCH2CH 3), 1.60-1.70 (4 H, m, CH 2CH 2), 2.75 (2 H, t, J = 7.0 Hz, ArCH2), 4.28 (2 H, t, J = 7.0 Hz, OCH 2CH3), 6.40 (1 H, d, J = 15.0 Hz, COCH=), 7.10-7.70 (4 H, m, ArH), 8.04 (1 H, d, J = 15.0 Hz, ArCH=) ppm. ¹³C NMR (90 MHz, CDCl3): δ = 13.9 (CH3), 14.3 (CH3), 22.5 (CH2), 25.6 (CH2), 33.8 (CH2), 60.5 (CH2), 119.3 (CH), 126.5 (CH), 127.3 (CH), 128.6 (CH), 130.0 (CH), 133.7 (C), 134.0 (C), 142.3 (CH), 168.0 (C) ppm.
Butylaromatic Compound 10c
¹H NMR (360 MHz, CDCl3): δ = 0.96 [3 H, t, J = 7.0 Hz, (CH2)2CH 3], 1.30 (3 H, t, J = 7.5 Hz, OCH2CH 3), 1.33 (2 H, m, CH2CH 2CH3), 1.62 (2 H, app. pent., J = ca. 7 Hz, CH2CH 2CH2) 1.71 (3 H, s, CH=CCH 3), 2.20-2.40 (4 H, m, CH2CH2CO2Et), 2.55 (2 H, t, J = 7.0 Hz, ArCH2), 3.22 (2 H, d, J = 6.0 Hz, ArCH 2CH=), 4.12 (2 H, q, J = 7.5 Hz, OCH 2CH3), 5.80 (1 H, t, J = 6.0 Hz, =CHCH2), 6.90-7.05 (4 H, m, ArH) ppm. ¹³C NMR (90 MHz, CDCl3): δ = 14.1 (2 × CH3), 17.1 (CH3), 22.4 (CH2), 29.6 (CH2), 31.9 (CH2), 33.8 (CH2), 34.6 (CH2), 35.2 (CH2), 61.3 (CH2), 122.8 (CH), 125.6 (CH), 125.9 (CH), 128.1 (CH), 128.9 (CH), 135.5 (C), 136.5 (C), 136.6 (C), 173.1 (C) ppm.
Arylvinylcyclopropane 9b
¹H NMR (360 MHz, CDCl3): δ = 1.15-1.30 (2 H, m, CHCH 2CH), 1.60 (3 H, t, J = 7.0 Hz, CH2CH 3), 1.60-1.75 (1 H, m, CHCH2CH), 2.10-2.20 (1 H, m, CHCH2CH), 4.30 (2 H, q, J = 7.0 Hz, CH 2CH3), 5.10 (1 H, d, J = 11.0 Hz, CH=CHH), 5.20 (1 H, d, J = 16.0 Hz, CH=CHH), 5.70 (1 H, ddd, J = 16.0, 11.0, 8.0 Hz, CH=CH2), 6.40 (1 H, d, J = 15.0 Hz, ArCH=CH), 7.00-7.60 (4 H, m, ArH), 8.30 (1 H, d, J = 15.0 Hz, ArCH=CH) ppm.
Vinylcyclopropane 9c
IR (CHCl3): νmax = 3011 (s), 1727 (s), 1634 (m), 1602 (w) cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 1.05 (1 H, app dt, J = 8.5, 5.0Hz, ArCHCHH), 1.22 (3 H, t, J = 7.0 Hz, OCH2CH 3), 1.24-1.27 (1 H, m, ArCHCHH), 1.54-1.59 (1 H, m, H2C=CHCH), 1.72 (3 H, app s, C=CCH3), 1.96 (1 H, ddd, J = 8.5, 5.5, 5.0 Hz, ArCH), 2.36 (2 H, t, J = 7.0Hz, O=CCH2CH 2), 2.43 (2 H, t, J = 7.0 Hz, O=CCH 2CH2), 3.43 (1 H, dd, J = 16.0, 7.0 Hz, ArCHH), 3.49 (1 H, dd, J = 16.0, 7.0 Hz, ArCHH), 4.10 (2 H, q, J = 7.0 Hz, OCH 2CH3), 4.96 (1 H, dd, J = 10.0, 1.5 Hz, HC=CHH), 5.13 (1 H, dd, J = 17.0, 1.5 Hz, HC=CHH), 5.34 (1 H, app tq, J = 7.0, 1.5 Hz, C=CH), 5.58 (1 H, ddd, J = 17.0, 10.0, 8.5 Hz, H2C=CH), 6.99 (1 H, dd, J = 6.0, 2.0 Hz, ArH), 7.12-7.15 (3 H, m, 3 × ArH) ppm. ¹³C NMR (100 MHz, CDCl3): δ = 14.2 (CH3), 14.6 (CH2), 16.2 (CH3), 23.0 (CH), 25.7 (CH), 31.6 (CH2), 33.2 (CH2), 34.7 (CH2), 60.3 (CH2), 112.4 (CH2), 123.6 (CH), 125.7, 126.0, 126.1 (3 × CH), 128.4 (CH), 134.4 (C), 139.5 (C), 140.9 (C), 141.0 (CH), 173.4 (C) ppm.
MS (ES): m/z C20H26O2Na [M + Na+]: 321.1825; found: 321.1817.