Three-Component Barbier Allylation, Friedel-Crafts Alkylation and Intramolecular Hydroalkoxylation in an Ionic Liquid for the Direct Synthesis of 4-Arylchromans

Abstract

4-Arylchromans can be synthesized directly using a one-pot Barbier allylation, Friedel-Crafts alkylation and intramolecular hydroalkoxylation of aromatic aldehydes, allylbromides and ­phenols in an ionic liquid (BPyX-SnCl₂·2H₂O). The intramolecular hydroalkoxylation of 4-aryl-4-(2-hydroxylphenyl)but-1-enes can be promoted using the Lewis acid ZnCl₂ in an ionic liquid.

Barbier - Friedel-Crafts - hydroalkoxylation - one-pot process - 4-arylchroman - ionic liquid

References and Notes

<A NAME="RW25906ST-1A">1a</A> Browers WS. Ohta T. Cleere JS. Marsella PA. Science  1976,  193:  542 

<A NAME="RW25906ST-1B">1b</A> Ellis GP. Lockhart IM. Chromanes and Tocopherols   Wiley-Interscience; New York: 1981. 

<A NAME="RW25906ST-2">2</A> Ogundaini A. Farah M. Perera P. J. Nat. Prod.  1996,  59:  587 

<A NAME="RW25906ST-3">3</A> Hajela K. Pandey J. Dwivedy A. Dhar JD. Sarkhel S. Maulik PR. Velumurugan D. Bioorg. Med. Chem.  1999,  7:  2083 

<A NAME="RW25906ST-4">4</A> Quaglia W. Pigini M. Piergentili A. Giannella M. Gentilli F. Marrucci G. Carrieri A. Carotti A. Pogges E. Leonardi A. Melchiorre C. J. Med. Chem.  2002,  45:  1633 

<A NAME="RW25906ST-5A">5a</A> Deng J.-Z. Starck SR. Li S. Hecht SM. J. Nat. Prod.  2005,  68:  1625 

<A NAME="RW25906ST-5B">5b</A> Maloney DJ. Starck SR. Gao Z. Hechit SM. J. Am. Chem. Soc.  2005,  127:  4140 

<A NAME="RW25906ST-5C">5c</A> Sawadjoon S. Kittikara K. Vichai V. Tanticharoen M. Thebta-Ranonth Y. J. Org. Chem.  2002,  67:  5470 

For example, see:

<A NAME="RW25906ST-6A">6a</A> Larock RC. Yang H. Pace P. Tetrahedron Lett.  1998,  39:  237 

<A NAME="RW25906ST-6B">6b</A> Trost BM. Asakawa N. Synthesis  1999,  1491 

<A NAME="RW25906ST-6C">6c</A> Nicolaou KC. Pfefferkorn JA. Barluenga S. Mitchell HJ. Roecker AJ. Cao G.-Q. J. Am. Chem. Soc.  2000,  122:  9968 

<A NAME="RW25906ST-6D">6d</A> Barluenga J. Trincado M. Rubio E. Gonzalez JM. J. Am. Chem. Soc.  2004,  126:  3416 

<A NAME="RW25906ST-6E">6e</A> Merchaet A. Delbeke P. Daloze D. Dive G. Tetrahedron Lett.  2004,  45:  4697 

<A NAME="RW25906ST-6F">6f</A> Trost BM. Shen HC. Surivet J.-P. J. Am. Chem. Soc.  2004,  126:  12565 

<A NAME="RW25906ST-6G">6g</A> Vyvyan JR. Oaksmith JM. Parks BW. Peterson EM. Tetrahedron Lett.  2005,  46:  2457 

<A NAME="RW25906ST-7A">7a</A> Shiina I. Suzuki M. Yokoyama K. Tetrahedron Lett.  2002,  43:  6395 

<A NAME="RW25906ST-7B">7b</A> Shiina I. Suzuki M. Yokoyama K. Tetrahedron Lett.  2004,  45:  965 

<A NAME="RW25906ST-7C">7c</A> Mertines K. Iovel I. Kischel J. Zapf A. Beller M. Angew. Chem. Int. Ed.  2005,  44:  238 

<A NAME="RW25906ST-8">8</A> For a review on the Barbier reaction, see: Yamamoto Y. Asao N. Chem. Rev.  1993,  93:  2207 

<A NAME="RW25906ST-9A">9a</A> Multicomponent Reactions   Zhu J. Bienayme H. Wiley-VCH; Weinheim: 2005. 

<A NAME="RW25906ST-9B">9b</A> Tietze LF. Chem. Rev.  1996,  96:  115 

<A NAME="RW25906ST-10">10</A> Zhao XL. Liu L. Chen YJ. Wang D. Tetrahedron  2006,  62:  7113 

<A NAME="RW25906ST-11A">11a</A> Masuyama Y. Kishida M. Kurusu Y. Tetrahedron Lett.  1996,  37:  7103 

<A NAME="RW25906ST-11B">11b</A> Masuyama Y. Ito A. Kurusu Y. Chem. Commun.  1998,  315 

<A NAME="RW25906ST-11C">11c</A> Masuyama Y. Ito T. Tachi K. Ito A. Kurusu Y. Chem. Commun.  1999,  1261 

<A NAME="RW25906ST-11D">11d</A> Ito A. Kishida M. Kurusu Y. Masuyama Y. J. Org. Chem.  2000,  65:  494 

<A NAME="RW25906ST-12">12</A> Wasserscheid P. Waffenschmidt H. J. Mol. Catal. A: Chem.  2000,  164:  61 

For examples of three-component reactions in ionic liquid, see:

<A NAME="RW25906ST-13A">13a</A> Aza-Diels-Alder reaction: Yadav JS. Reddy BVS. Reddy JSS. Rao RS. Tetrahedron  2003,  59:  1599 

<A NAME="RW25906ST-13B">13b</A> Coupling reaction of aldehyde, alkyne and amine: Li Z. Wei C. Chen L. Varma RS. Li C.-J. Tetrahedron Lett.  2004,  45:  2443 

<A NAME="RW25906ST-13C">13c</A> Mannich reaction: Kabalka GW. Venkataiah B. Dong G. Tetrahedron Lett.  2004,  45:  729 

<A NAME="RW25906ST-13D">13d</A> Asymmetric Mannich reaction: Chen S.-L. Ji S.-J. Loh T.-P. Tetrahedron Lett.  2003,  44:  2405 

<A NAME="RW25906ST-13E">13e</A> Biginelli reaction: Peng J. Deng Y. Tetrahedron Lett.  2001,  42:  5917 

<A NAME="RW25906ST-14A">14a</A> Coulombel L. Dunach E. Green Chem.  2004,  6:  499 

<A NAME="RW25906ST-14B">14b</A> Rosenfeld DC. Shekhar S. Takemiya A. Utsunomiya M. Hartwig JF. Org. Lett.  2006,  8:  4179 

<A NAME="RW25906ST-15">15</A> Bolzoni L. Casiraghi G. Casnati G. Sartori G. Angew. Chem., Int. Ed. Engl.  1978,  17:  684 

<A NAME="RW25906ST-16">16</A> Morimoto T. Takaki K. Angew. Chem. Int. Ed.  2006,  45:  2930 

<A NAME="RW25906ST-17">17</A> Talyor JG. Whittall N. Hii KK. Chem. Commun.  2005,  5103 

<A NAME="RW25906ST-18">18</A> Coulombel Favier I. Dunach E. Chem. Commun.  2005,  2286 

For examples, see:

<A NAME="RW25906ST-19A">19a</A> Bienayme H. Ancel J.-E. Meilland P. Simonato J.-P. Tetrahedron Lett.  2000,  41:  3339 

<A NAME="RW25906ST-19B">19b</A> Qian H. Han X. Widenhoefer RA. J. Am. Chem. Soc.  2004,  126:  9536 

<A NAME="RW25906ST-19C">19c</A> Oe Y. Ito Y. Chem. Commun.  2004,  1620 

<A NAME="RW25906ST-19D">19d</A> Yang C.-G. He Ch. J. Am. Chem. Soc.  2005,  127:  6966 

<A NAME="RW25906ST-19E">19e</A> Gligorich KM. Schultz MJ. Sigman MS. J. Am. Chem. Soc.  2006,  128:  2794 

<A NAME="RW25906ST-20">20</A> Talluri SK. Sudalai A. Org. Lett.  2005,  7:  855 

<A NAME="RW25906ST-21">21</A> Nguyen R.-V. Yao X. Li Ch.-J. Org. Lett.  2006,  8:  2397 

<A NAME="RW25906ST-22">22</A> Youn SW. Eom JI. J. Org. Chem.  2006,  71:  6705 

<A NAME="RW25906ST-23">23</A>

2-Methyl-4-(4′-hydroxylphenyl)chroman (8a): A mixture of salicylaldehyde 6a (61 mg, 0.5 mmol), allyl bromide (2a) (120 mg, 1 mmol) and phenol 3a (69 mg, 0.75 mmol) in ionic liquid (10a) derived from BPyCl-SnCl₂·2H₂O was stirred at ambient temperature for 10 h. ZnCl₂ (102 mg, 0.75 mmol) was added, followed by stirring at 70 °C for 5 h. The reaction mixture was extracted with Et₂O. The combined Et₂O extracts were washed with aqueous HCl (2 M), and then dried over Na₂SO₄. The solvent was removed under vacuum and the crude product was purified by flash column chromatography on silica gel (EtOAc-PE, 1:30) to afford 8a as a colorless oil (84 mg, 70%); FTIR (film): 3394, 2971, 1649, 1612, 1581, 1514, 1483, 1455, 1232 cm^-1; ¹H NMR (300 MHz, CDCl₃): δ = 7.10-7.30 (m, 6 H), 6.72-7.07 (m, 2 H), 4.12-4.34 (m, 2 H), 1.91-1.26 (m, 2 H), 1.38, 1.48 (2 × d, J = 6.9, 6.2 Hz, 3 H); ¹³C NMR (75 MHz, CDCl₃): δ = 154.9, 153.9 (153.6)*, 138.6, 136.7, 130.5, 129.4, 129.3, 127.2 (127.6), 125.7, 120.0, 116.2 (116.5), 114.8 (115.2), 67.2 (72.2), 41.8 (38.8), 39.7 (37.5), 20.7 (21.1); (* data in parentheses represents diastereomeric peaks); HRMS (EI): m/z calcd for C₁₆H₁₆O₂: 240.1150; found: 240.1149.

<A NAME="RW25906ST-24">24</A>

2,2-Dimethyl-4-(4′-hydroxylphenyl)chroman (9a): A mixture of salicylaldehyde 6a (61 mg, 0.5 mmol), 2-methyl-allyl chloride (2b) (82 mg, 1.0 mmol) and phenol 3e (69 mg, 0.75 mmol) in ionic liquid (10b) derived from BPyI-SnCl₂·2H₂O was stirred at 40 °C for 24 h. The reaction mixture was extracted with Et₂O. The combined Et₂O phase was washed with aqueous HCl (2 M), then dried over Na₂SO₄. The solvent was removed under vacuum and the crude product was purified by flash column chromatography on silica gel (EtOAc-PE, 1:30) to afford 9a as a colorless oil (83 mg, 66%); FTIR (film): 3394, 2925, 1612, 1571, 1514, 1486, 1449, 1368, 1253, 1124 cm^-1; ¹H NMR (300 MHz CDCl₃): δ = 7.01-7.16 (m, 3 H), 6.69-6.88 (m, 5 H), 5.63 (br s, 1 H), 4.01 (dd, J = 7.2, 4.8 Hz, 1 H), 2.08-2.33 (m, 2 H), 1.43 (s, 3 H), 1.36 (s, 3 H); ¹³C NMR (75 MHz, CDCl₃): δ = 154.6, 154.2, 137.1, 129.9, 127.7, 125.0, 119.9, 117.2, 115.5, 74.8, 43.6, 39.1, 30.0, 24.3; HRMS (EI): m/z calcd for C₁₇H₁₈O₂: 254.1307; found: 254.1308.

<A NAME="RW25906ST-25">25</A> Ito A. Kishida M. Kurusu Y. Masuyama Y. J. Org. Chem.  2000,  65:  494