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

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Synlett 2005(12): 1877-1880
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;

Further Information

Publication History

Received 20 April 2005
Publication Date:
07 July 2005 (online)

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

References

1a Keck GE. Enholm EJ. Yates JB. Wiley MR. Tetrahedron 1985, 41: 4079

Crossref PubMed Google Scholar
1b Farina V. Pure. Appl. Chem. 1996, 68: 73

Crossref PubMed Google Scholar
1c Varma RS. Naicker KP. Green Chem. 1999, 247

Crossref PubMed Google Scholar
1d Maruyama K. Imahori H. Osuka A. Takuwa A. Tagawa H. Chem. Lett. 1986, 1719

Crossref PubMed Google Scholar
1e Hanamoto T. Kobayashi T. Kondo M. Synlett 2001, 281

Crossref PubMed Google Scholar
1f Negishi E. J. Organomet. Chem. 2002, 653: 34

Crossref PubMed Google Scholar
1g Lipshutz BH. Frieman B. Pfeiffer SS. Synthesis 2002, 2110

Crossref PubMed Google Scholar
1h Ramachandran PV. Aldrichimica Acta 2002, 35: 23

Crossref PubMed Google Scholar
1i Tivola PB. Deagostino A. Prandi C. Venturello P. Org. Lett. 2002, 4: 1275

Crossref PubMed Google Scholar
1j Lopez-Ruiz H. Zard SZ. Chem. Commun. 2001, 2618

Crossref PubMed Google Scholar
1k Goldberg SD. Grubbs RH. Angew. Chem. Int. Ed. 2002, 41: 807

Crossref PubMed Google Scholar
1l Yamamoto Y. Takahashi M. Miyaura N. Synlett 2002, 1473

Crossref PubMed Google Scholar
1m Uozumi Y. Danjo H. Hayashi T. J. Org. Chem. 1999, 64: 3384

Crossref PubMed Google Scholar
2a Keck GE. Yates JB. J. Org. Chem. 1982, 47: 3590

Google Scholar
2b 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

Google Scholar
3 Stefinovic M. Snieckus V. J. Org. Chem. 1998, 63: 2808

Crossref Google Scholar
4 Miller SJ. Blackwell HE. Grubbs RH. J. Am. Chem. Soc. 1996, 118: 9606

Crossref Google Scholar
5a Handbook of Metathesis Vol. 1-3: Grubbs RH. Wiley-VCH; Berlin: 2003.

Google Scholar
5b Kotha S. Sreenivasachary N. Indian J. Chem., Sect. B 2001, 40: 763

Google Scholar
6a Schuster M. Blechert S. Angew. Chem., Int. Ed. Engl. 1997, 36: 2036

Google Scholar
6b Phillips AJ. Abell AD. Aldrichimica Acta 1999, 32: 75

Google Scholar
6c Vernall AJ. Abell AD. Aldrichimica Acta 2003, 36: 93

Google Scholar
7a Okada A. Ohshima T. Shibasaki M. Tetrahedron Lett. 2001, 42: 8023

Google Scholar
7b Feng J. Schuster M. Blechert S. Synlett 1997, 12

Google Scholar
8a Ek F. Axelsson O. Wistrand LG. Frejd T. J. Org. Chem. 2002, 67: 6376

Crossref Google Scholar
8b Tiley JW. Sarabu R. Wanger R. Mulkerins K. J. Org. Chem. 1990, 55: 906

Crossref Google Scholar
8c Yamaguchi R. Otsuji A. Utimoto K. Kozima S. Bull. Chem. Soc. Jpn. 1992, 65: 298

Crossref Google Scholar
8d Gryko DT. Clausen C. Roth KM. Dontha N. Bocian DF. Kuhr WG. Lindsey JS. J. Org. Chem. 2000, 65: 7345

Crossref Google Scholar
9 Wenkert E. Fersnandes JB. Michelotti EL. Swindell CS. Synthesis 1983, 701

Article in Thieme Connect Google Scholar
10 Abbritti G. Matteis FD. Chem. Biol. Interact. 1972, 4: 281

Crossref Google Scholar
11a Troisi L. Florio S. Granito C. Steroids 2002, 67: 687

Crossref Google Scholar
11b Nemoto H. Satoh A. Fukumoto K. Tetrahedron 1995, 51: 10159

Crossref Google Scholar
12 Brown MA. Kerr MA. Tetrahedron Lett. 2001, 42: 983

Crossref Google Scholar
13 Ochiai M. Arimoto M. Fujita E. Tetrahedron Lett. 1981, 22: 4491

Crossref Google Scholar
14 Price CC. Org. React. 1946, 3: 1

Google Scholar
15 Kodomari M. Nawa S. Miyoshi T. J. Chem. Soc., Chem. Commun. 1995, 1895

Crossref Google Scholar
16 Snieckus VA. Chem. Rev. 1990, 90: 879

Google Scholar
17a Stille JK. Angew. Chem., Int. Ed. Engl. 1985, 25: 508

Google Scholar
17b Miyaura N. Suzuki A. Chem. Rev. 1995, 95: 2457

Google Scholar
18 Heck RF. J. Am. Chem. Soc. 1968, 90: 5531

Crossref Google Scholar
19 Kosugi M. Sasazawa K. Shimizu Y. Migita T. Chem. Lett. 1977, 301

Crossref Google Scholar
20a Kotha S. Lahiri K. Kashinath D. Tetrahedron 2002, 58: 9633

Crossref Google Scholar
20b Suzuki A. Brown HC. Organic Synthesis via Boranes Vol. 3: Aldrich Chemical Company Inc.; Milwaukee, USA: 2003.

Crossref Google Scholar
21 Molander GA. Yun C.-S. Tetrahedron 2002, 58: 1465

Crossref Google Scholar
22 For review on B-alkyl Suzuki-Miyaura cross-coupling reaction see: Chemler SR. Trauner D. Danishefsky SJ. Angew. Chem. Int. Ed. 2001, 40: 4544

Crossref Google Scholar
23 Occhiato EG. Trabocchi A. Guarna A. J. Org. Chem. 2001, 66: 2459

Google Scholar
24a Kalinin VN. Denisov FS. Bubnov YN. Mendeleev Commun. 1996, 206

Google Scholar
24b Nilsson K. Hallberg A. Acta Chem. Scand. Ser. B 1987, 41: 569

Google Scholar
25a Fürstner A. Seidel G. Synlett 1998, 161

Google Scholar
25b Fürstner A. Leitner A. Synlett 2001, 290

Google Scholar
26 Margaretha P. Reichow S. Agosta WC. J. Org. Chem. 1994, 59: 5393

Crossref Google Scholar
27 Desurmont G. Dalton S. Giolando DM. Srebnik M. J. Org. Chem. 1996, 61: 7943

Crossref Google Scholar
28 Bouyssi D. Gerusz V. Balme G. Eur. J. Org. Chem. 2002, 2445

Crossref Google Scholar
32 Roush WR. Walts AE. Hoong LK. J. Am. Chem. Soc. 1985, 107: 8186 ; we have adopted this procedure for the preparation of 2b

Crossref Google Scholar
33 Tilley JW. Sarabu R. Wagner R. Mulkerins K. J. Org. Chem. 1990, 55: 906

Crossref Google Scholar
34 Ek F. Axelsson O. Wistrand L.-G. Frejd T. J. Org. Chem. 2002, 67: 6376

Crossref Google Scholar
35 Lee PH. Sung S.-Y. Lee K. Org. Lett. 2001, 3: 3201

Crossref Google Scholar
36 Echavarren AM. Stille JK. J. Am. Chem. Soc. 1988, 110: 1557

Crossref Google Scholar
37 Gomes P. Gosmini C. Perichon J. Org. Lett. 2003, 5: 1043

Crossref Google Scholar
38 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

Crossref Google Scholar
40 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

Crossref Google Scholar

29

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.

30

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.

31

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

39

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.