A Simple Synthetic Approach to Allylated Aromatics via the Suzuki-Miyaura Cross-Coupling Reaction

Sambasivarao Kotha; Manoranjan Behera; Vrajesh R. Shah

doi:10.1055/s-2005-871569

LETTER

A Simple Synthetic Approach to Allylated Aromatics via the Suzuki-Miyaura Cross-Coupling Reaction

Sambasivarao Kotha*, Manoranjan Behera, Vrajesh R. Shah
Department of Chemistry, Indian Institute of Technology-Bombay, Powai, Mumbai - 400 076, India
Fax: +91(22)25723480; e-Mail: srk@chem.iitb.ac.in;

Abstract

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Abstract

The Pd-catalyzed cross-coupling reaction of aromatic iodides and bromides with allylboronic acid esters (2a,b) in the presence of CsF gave allylated aromatics.

Key words

allylation - palladium - boron - cross-coupling reaction - Suzuki coupling

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References

<A NAME="RD10405ST-1A">1a</A> Keck GE. Enholm EJ. Yates JB. Wiley MR. Tetrahedron 1985, 41: 4079

<A NAME="RD10405ST-1B">1b</A> Farina V. Pure. Appl. Chem. 1996, 68: 73

<A NAME="RD10405ST-1C">1c</A> Varma RS. Naicker KP. Green Chem. 1999, 247

<A NAME="RD10405ST-1D">1d</A> Maruyama K. Imahori H. Osuka A. Takuwa A. Tagawa H. Chem. Lett. 1986, 1719

<A NAME="RD10405ST-1E">1e</A> Hanamoto T. Kobayashi T. Kondo M. Synlett 2001, 281

<A NAME="RD10405ST-1F">1f</A> Negishi E. J. Organomet. Chem. 2002, 653: 34

<A NAME="RD10405ST-1G">1g</A> Lipshutz BH. Frieman B. Pfeiffer SS. Synthesis 2002, 2110

<A NAME="RD10405ST-1H">1h</A> Ramachandran PV. Aldrichimica Acta 2002, 35: 23

<A NAME="RD10405ST-1I">1i</A> Tivola PB. Deagostino A. Prandi C. Venturello P. Org. Lett. 2002, 4: 1275

<A NAME="RD10405ST-1J">1j</A> Lopez-Ruiz H. Zard SZ. Chem. Commun. 2001, 2618

<A NAME="RD10405ST-1K">1k</A> Goldberg SD. Grubbs RH. Angew. Chem. Int. Ed. 2002, 41: 807

<A NAME="RD10405ST-1L">1l</A> Yamamoto Y. Takahashi M. Miyaura N. Synlett 2002, 1473

<A NAME="RD10405ST-1M">1m</A> Uozumi Y. Danjo H. Hayashi T. J. Org. Chem. 1999, 64: 3384

<A NAME="RD10405ST-2A">2a</A> Keck GE. Yates JB. J. Org. Chem. 1982, 47: 3590

<A NAME="RD10405ST-2B">2b</A> Bertrand F. Guyader FL. Liguori L. Ouvry G. Quiclet-Sire B. Seguin S. Zard SZ. C. R. Acad. Sci., Ser. IIc: Chim. 2001, 4: 547

<A NAME="RD10405ST-3">3</A> Stefinovic M. Snieckus V. J. Org. Chem. 1998, 63: 2808

<A NAME="RD10405ST-4">4</A> Miller SJ. Blackwell HE. Grubbs RH. J. Am. Chem. Soc. 1996, 118: 9606

<A NAME="RD10405ST-5A">5a</A> Handbook of Metathesis Vol. 1-3: Grubbs RH. Wiley-VCH; Berlin: 2003.

<A NAME="RD10405ST-5B">5b</A> Kotha S. Sreenivasachary N. Indian J. Chem., Sect. B 2001, 40: 763

<A NAME="RD10405ST-6A">6a</A> Schuster M. Blechert S. Angew. Chem., Int. Ed. Engl. 1997, 36: 2036

<A NAME="RD10405ST-6B">6b</A> Phillips AJ. Abell AD. Aldrichimica Acta 1999, 32: 75

<A NAME="RD10405ST-6C">6c</A> Vernall AJ. Abell AD. Aldrichimica Acta 2003, 36: 93

<A NAME="RD10405ST-7A">7a</A> Okada A. Ohshima T. Shibasaki M. Tetrahedron Lett. 2001, 42: 8023

<A NAME="RD10405ST-7B">7b</A> Feng J. Schuster M. Blechert S. Synlett 1997, 12

<A NAME="RD10405ST-8A">8a</A> Ek F. Axelsson O. Wistrand LG. Frejd T. J. Org. Chem. 2002, 67: 6376

<A NAME="RD10405ST-8B">8b</A> Tiley JW. Sarabu R. Wanger R. Mulkerins K. J. Org. Chem. 1990, 55: 906

<A NAME="RD10405ST-8C">8c</A> Yamaguchi R. Otsuji A. Utimoto K. Kozima S. Bull. Chem. Soc. Jpn. 1992, 65: 298

<A NAME="RD10405ST-8D">8d</A> Gryko DT. Clausen C. Roth KM. Dontha N. Bocian DF. Kuhr WG. Lindsey JS. J. Org. Chem. 2000, 65: 7345

<A NAME="RD10405ST-9">9</A> Wenkert E. Fersnandes JB. Michelotti EL. Swindell CS. Synthesis 1983, 701

<A NAME="RD10405ST-10">10</A> Abbritti G. Matteis FD. Chem. Biol. Interact. 1972, 4: 281

<A NAME="RD10405ST-11A">11a</A> Troisi L. Florio S. Granito C. Steroids 2002, 67: 687

<A NAME="RD10405ST-11B">11b</A> Nemoto H. Satoh A. Fukumoto K. Tetrahedron 1995, 51: 10159

<A NAME="RD10405ST-12">12</A> Brown MA. Kerr MA. Tetrahedron Lett. 2001, 42: 983

<A NAME="RD10405ST-13">13</A> Ochiai M. Arimoto M. Fujita E. Tetrahedron Lett. 1981, 22: 4491

<A NAME="RD10405ST-14">14</A> Price CC. Org. React. 1946, 3: 1

<A NAME="RD10405ST-15">15</A> Kodomari M. Nawa S. Miyoshi T. J. Chem. Soc., Chem. Commun. 1995, 1895

<A NAME="RD10405ST-16">16</A> Snieckus VA. Chem. Rev. 1990, 90: 879

<A NAME="RD10405ST-17A">17a</A> Stille JK. Angew. Chem., Int. Ed. Engl. 1985, 25: 508

<A NAME="RD10405ST-17B">17b</A> Miyaura N. Suzuki A. Chem. Rev. 1995, 95: 2457

<A NAME="RD10405ST-18">18</A> Heck RF. J. Am. Chem. Soc. 1968, 90: 5531

<A NAME="RD10405ST-19">19</A> Kosugi M. Sasazawa K. Shimizu Y. Migita T. Chem. Lett. 1977, 301

<A NAME="RD10405ST-20A">20a</A> Kotha S. Lahiri K. Kashinath D. Tetrahedron 2002, 58: 9633

<A NAME="RD10405ST-20B">20b</A> Suzuki A. Brown HC. Organic Synthesis via Boranes Vol. 3: Aldrich Chemical Company Inc.; Milwaukee, USA: 2003.

<A NAME="RD10405ST-21">21</A> Molander GA. Yun C.-S. Tetrahedron 2002, 58: 1465

<A NAME="RD10405ST-22">22</A> For review on B-alkyl Suzuki-Miyaura cross-coupling reaction see: Chemler SR. Trauner D. Danishefsky SJ. Angew. Chem. Int. Ed. 2001, 40: 4544

<A NAME="RD10405ST-23">23</A> Occhiato EG. Trabocchi A. Guarna A. J. Org. Chem. 2001, 66: 2459

<A NAME="RD10405ST-24A">24a</A> Kalinin VN. Denisov FS. Bubnov YN. Mendeleev Commun. 1996, 206

<A NAME="RD10405ST-24B">24b</A> Nilsson K. Hallberg A. Acta Chem. Scand. Ser. B 1987, 41: 569

<A NAME="RD10405ST-25A">25a</A> Fürstner A. Seidel G. Synlett 1998, 161

<A NAME="RD10405ST-25B">25b</A> Fürstner A. Leitner A. Synlett 2001, 290

<A NAME="RD10405ST-26">26</A> Margaretha P. Reichow S. Agosta WC. J. Org. Chem. 1994, 59: 5393

<A NAME="RD10405ST-27">27</A> Desurmont G. Dalton S. Giolando DM. Srebnik M. J. Org. Chem. 1996, 61: 7943

<A NAME="RD10405ST-28">28</A> Bouyssi D. Gerusz V. Balme G. Eur. J. Org. Chem. 2002, 2445

Representative Experimental Procedure for Cross-Coupling Reaction.
A two-neck round-bottom flask was charged diiodo compound 1 (0.049 mmol), CsF (0.19 mmol), Pd(PPh₃)₄ (5-10 mol%) in THF (3 mL) and stirred for 30 min. Allyl boronic acid pinacol ester 2a (0.176 mmol) in THF (3 mL) was added and the resulting reaction mixture was heated to reflux for 24 h. Then, another portion of CsF (0.19 mmol) and Pd(PPh₃)₄ (5-10 mol%) were added and reaction was continued. At the end of the reaction (TLC monitoring), the reaction mixture was diluted with petroleum ether (bp 60-80 °C, 10 mL) followed by H₂O. The layers were separated and the aqueous layer was extracted with petroleum ether (2 × 10 mL). The combined organic layers were washed with H₂O (20 mL), brine (20 mL) and dried (Na₂SO₄). Evaporation of the solvent gave the crude product, which was purified by silica gel column chromatography. Elution of the column with 10% EtOAc-petroleum ether gave the diallylated product 3 (90%) as a white solid which was characterized by spectral data.

Spectral Data for Compound 3. Mp 64-68 °C. IR (neat): 3404, 1728, 1672 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.40 (t, 3 H, J = 7.4 Hz), 3.21-3.40 (m, 6 H), 3.70 (d, 2 H, J = 14.9 Hz), 4.30 (q, 2 H, J = 7.4 Hz), 5.00-5.12 (m, 4 H), 5.81-6.12 (m, 2 H), 6.22 (s, 1 H), 7.00-7.21 (m, 8 H), 8.21 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 14.2, 39.8, 40.7, 62.2, 67.6, 115.8, 128.5, 129.8, 133.7, 137.3, 138.8, 160.8, 172.0. HRMS (FAB): m/z [M + H]⁺ calcd for C₂₅H₂₉NO₃: 392.2226; found: 392.2231.

Compounds 4, [33] 6, [34] 7, [35] 9, [36] 10, [37] 11, [38] 12 [40] are reported in literature by different routes.

<A NAME="RD10405ST-32">32</A> Roush WR. Walts AE. Hoong LK. J. Am. Chem. Soc. 1985, 107: 8186 ; we have adopted this procedure for the preparation of 2b

<A NAME="RD10405ST-33">33</A> Tilley JW. Sarabu R. Wagner R. Mulkerins K. J. Org. Chem. 1990, 55: 906

<A NAME="RD10405ST-34">34</A> Ek F. Axelsson O. Wistrand L.-G. Frejd T. J. Org. Chem. 2002, 67: 6376

<A NAME="RD10405ST-35">35</A> Lee PH. Sung S.-Y. Lee K. Org. Lett. 2001, 3: 3201

<A NAME="RD10405ST-36">36</A> Echavarren AM. Stille JK. J. Am. Chem. Soc. 1988, 110: 1557

<A NAME="RD10405ST-37">37</A> Gomes P. Gosmini C. Perichon J. Org. Lett. 2003, 5: 1043

<A NAME="RD10405ST-38">38</A> Cheng X. Prehm M. Das MK. Kain J. Baumeister U. Diele S. Leine D. Blume A. Tschierske C. J. Am. Chem. Soc. 2003, 125: 10977

Spectral Data. Compound 5: IR (neat): 3020, 1720, 1608, 1502, 1086 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 3.40 (d, J = 6.5 Hz, 2 H), 3.81-3.96 (m, 6 H), 5.02-5.09 (m, 2 H), 5.91-6.00 (m, 1 H), 6.90 (d, J = 8.7 Hz, 1 H), 7.29 (s, 1 H), 7.60 (d, J = 8.7 Hz, 1 H). ¹³C NMR (75.4 MHz, CDCl₃): δ = 39.1, 52.1, 56.2, 112.2, 116.1, 119.8, 131.7, 133.7, 137.2, 157.6, 166.8. MS (EI, Q-TOF): m/z calcd for [C₁₂H₁₂O₃ + Na]: 229.0841; found: 229.0850.
Compound 8: IR (neat): ν_max = 1736, 1657, 1268, 1157, 1052 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 2.51 (s, 3 H), 3.59 (d, 2 H, J = 7.6 Hz), 5.15-5.22 (m, 2 H), 5.90-6.01 (m, 1 H), 6.84 (d, 1 H, J = 4.0 Hz), 7.55 (d, 1 H, J = 3.6 Hz). ¹³C NMR (75.4 MHz, CDCl₃): δ = 26.6, 34.9, 117.5, 126.1, 133.0, 135.2, 142.8, 152.9, 190.6. MS (EI, Q-TOF): m/z [M + H]⁺ calcd for C₉H₁₀OS: 167.0531; found: 167.0530.

<A NAME="RD10405ST-40">40</A> Liu Z. Yasseri AA. Loewe RS. Lysenko AB. Malinovskii VL. Zhao Q. Surthi S. Li Q. Misra V. Lindsey JS. Bocian DF. J. Org. Chem. 2004, 69: 5568