PDF herunterladen
Synlett 2011(17): 2590-2594  
DOI: 10.1055/s-0030-1289519
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Cationic Palladium(II)-Catalyzed Synthesis of 2-Substituted 3-Hydroxymethylbenzo[b]furans

Huan Wang, Xiuling Han*, Xiyan Lu*
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China
Fax: +86(21)64166128; e-Mail: xylu@mail.sioc.ac.cn;
Weitere Informationen

Publikationsverlauf

Received 29 July 2011
Publikationsdatum:
06. Oktober 2011 (online)

   Lizenzen und Reprints Alle Artikel dieser Rubrik
Preview

Abstract

A tandem reaction involving an intramolecular oxypalladation of an alkyne and an addition to the carbonyl group to quench the carbon-palladium bond to complete the catalytic cycle was developed. The reaction was catalyzed with the cationic palladium(II) species without the necessity of a redox system.

Key words

aldehyde - alkyne - cationic palladium(II) complex - 3-hydroxymethylbenzofuran - oxypalladation

    References and Notes

  • 1a Luca LD. Nieddu G. Porcheddu A. Giacomelli G. Curr. Med. Chem.  2009,  16:  1 
    Suche in Google Scholar
  • 1b Cagniant P. Carniant D. Adv. Heterocycl. Chem.  1975,  18:  337 
    Suche in Google Scholar
  • 2 Donnelly DMX. Meegan MJ. In Comprehensive Heterocyclic Chemistry   Vol. 4:  Katritzky AR. Rees CW. Pergamon Press; Oxford: 1984.  p.657-712  
    Suche in Google Scholar
  • 3a Graening T. Thrun F. In Comprehensive Heterocyclic Chemistry III   Vol. 3:  Katritzky AR. Elsevier; Amsterdam: 2008.  p.497-568  
    Suche in Google Scholar
  • 4a Alonso F. Beletskaya IP. Yus M. Chem. Rev.  2004,  104:  3079 
    Suche in Google Scholar
  • 4b Zeni G. Larock RC. Chem. Rev.  2004,  104:  2285 
    Suche in Google Scholar
  • 4c Nakamura I. Yamamoto Y. Chem. Rev.  2004,  104:  2127 
    Suche in Google Scholar
  • 4d Patil NT. Yamamoto Y. Chem. Rev.  2008,  108:  3395 
    Suche in Google Scholar
  • 4e Hosokawa T. Murahashi S. In Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E. John Wiley and Sons; New York: 2002.  p.2169-2172  
  • 5a Cacchi S. Fabrizi G. Moro L. Synlett  1998,  741 
  • 5b Monteiro N. Balme G. Synlett  1998,  746 
  • 6a Nan Y. Miao H. Yang Z. Org. Lett.  2000,  2:  297 
    Suche in Google Scholar
  • 6b Liao Y. Smith J. Fathi R. Yang Z. Org. Lett.  2005,  7:  2707 
    Suche in Google Scholar
  • 6c Liao Y. Reitman M. Zhang Y. Fathi R. Yang Z. Org. Lett.  2002,  4:  2607 
    Suche in Google Scholar
  • 6d Lütjens H. Scammells PJ. Synlett  1999,  1079 
  • 6e Lütjens H. Scammells PJ. Tetrahedron Lett.  1998,  39:  6581 
    Suche in Google Scholar
  • 6f KondoY . Shiga F. Murata N. Sakamoto T. Yamanaka H. Tetrahedron  1994,  50:  11803 
    Suche in Google Scholar
  • 7 Martínez C. Álvarez R. Aurrecoechea JM. Org. Lett.  2009,  11:  1083 
    CrossrefSuche in Google Scholar
  • 8a Zhao L. Lu X. Angew. Chem. Int. Ed.  2002,  41:  4343 
    Suche in Google Scholar
  • 8b Han X. Lu X. Org. Lett.  2010,  12:  3336 
    Suche in Google Scholar
  • 8c Han X. Lu X. Org. Lett.  2010,  12:  108 
    Suche in Google Scholar
  • 8d Liu G. Lu X. Adv. Synth. Catal.  2007,  349:  2247 
    Suche in Google Scholar
  • 8e Yang M. Zhang X. Lu X. Org. Lett.  2007,  9:  5131 
    Suche in Google Scholar
  • 8f Wang H. Han X. Lu X. Tetrahedron  2010,  66:  9129 
    Suche in Google Scholar
  • 9a Nakamura M. Ilies L. Otsubo S. Nakamura E. Org. Lett.  2006,  8:  2803 
    Suche in Google Scholar
  • 9b Nakamura M. Ilies L. Otsubo S. Nakamura E. Angew. Chem. Int. Ed.  2006,  45:  944 
    Suche in Google Scholar
  • 10a Zhang W. Wang PG. J. Org. Chem.  2000,  65:  4732 
    Suche in Google Scholar
  • 10b Carlsson B. Singh BN. Temciuc M. Nilsson S. Li Y.-L. Mellin C. Malm J. J. Med. Chem.  2002,  45:  623 
    Suche in Google Scholar
  • 11 Mikami K. Hatano M. Akiyama K. Top. Organomet. Chem.  2005,  14:  279 ; and references cited therein
    Suche in Google Scholar
  • 12 The paper reported that {Pd[(R)-Tol-BINAP](H2O)2}(BF4)2 could transform to {Pd[(R)-Tol-BINAP](µ-OH)}2(BF4)2 with 4 Å MS. It is possible that [Pd(dppp)(µ-OH)]2(BF4)2 formed in situ from [Pd(dppp)(H2O)2](BF4)2 and 4 Å MS is more active for the reaction. See: Fujii A. Hagiwara E. Sodeoka M. J. Am. Chem. Soc.  1999,  121:  5450 
    CrossrefSuche in Google Scholar
  • 13a Isono N. Lautens M. Org. Lett.  2009,  11:  1329 
    Suche in Google Scholar
  • 13b Belting V. Krause N. Org. Lett.  2006,  8:  4489 
    Suche in Google Scholar
  • 13c Li X. Chianese AR. Vogel T. Crabtree RH. Org. Lett.  2005,  7:  5437 
    Suche in Google Scholar
14

General Procedure for the Synthesis of 2-Substituted 3-Hydroxymethylbenzofuran Catalyzed by [Pd(dppp)(H 2 O) 2 ](BF 4 ) 2
A dried small tube with screw-cap was charged with [Pd(dppp)(H2O)2](BF4)2 (1.2 mg, 0.002 mmol), 4 Å MS
(20 mg), THF (0.5 mL), then substrates 1 (0.1 mmol) and aldehydes 2 (0.2 mmol, 2 equiv) were added to the mixture, and the solution was stirred at 45 ˚C until complete consumption of substrates 1 (monitored by TLC). Then,
the mixture was concentrated under reduced pressure and purified by flash column chromatography on silica gel
using EtOAc and PE as the eluent to afford the product.
Compound 3aa: solid; mp 87-89 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 8.16 (d, J = 8.8 Hz, 2 H), 7.77 (d, J = 6.8 Hz, 2 H), 7.65 (d, J = 8.4 Hz, 2 H), 7.52-7.45 (m, 4 H), 7.28-7.23 (m, 1 H), 7.19 (d, J = 7.6 Hz, 1 H), 7.08 (t, J = 7.6 Hz, 1 H), 6.39 (s, 1 H), 2.61 (d, J = 3.6 Hz, 1 H). ¹³C NMR (75 MHz, CDCl3): δ = 154.3, 153.5, 149.1, 147.1, 129.7, 129.5, 129.0, 127.7, 126.9, 124.9, 123.0, 121.0, 116.2, 111.4, 67.7. IR (KBr): ν = 3349, 3065, 1600, 1518, 1453, 1344, 1027, 834, 746 cm-¹. MS (EI): m/z (%) = 345 (100) [M+], 328, 223, 165, 105, 77, 57. HRMS (EI): m/z calcd for C21H15NO4: 345.1001; found: 345.1005.