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Synlett 2012(3): 375-380  
DOI: 10.1055/s-0031-1290203
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Palladium-Mediated Highly Regio- and Stereoselective Intermolecular β-Arylation on Allylic Alcohols: Synthesis of Functionalized Allylic Alcohols

J. Krishna, A. Gopi Krishna Reddy, B. Venkat Ramulu, L. Mahendar, G. Satyanarayana*
Indian Institute of Technology (IIT) Hyderabad, Ordnance Factory Estate Campus, Yeddumailaram 502 205, Medak District, Andhra Pradesh, India
Fax: +91(40)23016032; e-Mail: gvsatya@iith.ac.in;
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Publication History

Received 25 October 2011
Publication Date:
26 January 2012 (online)

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Abstract

An efficient and highly regio- and stereoselctive Pd-catalyzed β-arylation method for the formation of β-aryl allylic alcohols, employing aryl iodides, 1-bromo-2-iodobenzenes, and 2-bromobezaldehydes as coupling partners, is presented. The β-aryl allylic alcohols formed in this Pd-catalyzed transformation is unexpected under conventional Jeffery conditions without the assistance of silver salt. It is proposed that the reaction is substrate controlled, and the selective formation of the product depends on the size or nature of the substituent at the ortho position on the aromatic ring of the allylic alcohol part.

Key words

Pd catalysis - β-arylation - Mizoroki-Heck - allylic alcohols - β-carbonyls

    References

  • 1a Heck RF. J. Am. Chem. Soc.  1968,  90:  5526 
    Google Scholar
  • 1b Heck RF. Palladium Reagents in Organic Syntheses   Academic Press; London: 1985. 
    Google Scholar
  • 1c Heck RF. Org. React.  1982,  27:  345 
    Google Scholar
  • For selected reviews, see:
  • 2a Dounay AB. Overman LE. Chem. Rev.  2003,  103:  2945 
    Google Scholar
  • 2b Beletskaya IP. Cheprakov AV. Chem. Rev.  2000,  100:  3009 
    Google Scholar
  • 2c Tietze LF. Ila H. Bell HP. Chem. Rev.  2004,  104:  3453 
    Google Scholar
  • 2d Zeni G. Larock RC. Chem. Rev.  2006,  106:  4644 
    Google Scholar
  • 2e Negishi E. Copéret C. Ma S. Liou S.-Y. Liu F. Chem. Rev.  1996,  96:  365 
    Google Scholar
  • 3 Melpolder JB. Heck RF. J. Org. Chem.  1976,  41:  265 
    Google Scholar
  • 4 Chalk AJ. Magennis SA. J. Org. Chem.  1976,  41:  273 
    Google Scholar
  • 5a Jeffery T. Tetrahedron Lett.  1991,  32:  2121 
    Google Scholar
  • 5b Jeffery T. Tetrahedron Lett.  1990,  31:  6641 
    Google Scholar
  • 5c Jeffery T. J. Chem. Soc., Chem. Commun.  1991,  324 
    Google Scholar
  • 6 For the relevant topic, see review: Muzart J. Tetrahedron  2005,  61:  4179 
    Google Scholar
  • 7a Tamaru Y. Yamada Y. Yoshida Z. Tetrahedron  1979,  35:  329 
    Google Scholar
  • 7b Aslam M. Elango V. Davenport KG. Synthesis  1989,  869 
    Google Scholar
  • 7c Beller M. Zapf A. Synlett  1998,  792 
    Google Scholar
  • 7d Bouquillon S. Ganchegui B. Estrine B. Hénin F. Muzart J. J. Organomet. Chem.  2001,  634:  153 
    Google Scholar
  • 7e Caló V. Nacci A. Monopoli A. Spinelli M. Eur. J. Org. Chem.  2003,  1382 
    Google Scholar
  • 7f Jeffery T. J. Chem. Soc., Chem. Commun.  1984,  1287 
    Google Scholar
  • 7g Reymond J.-L. Jahangiri CK. Stoudt C. Lerner RA. J. Am. Chem. Soc.  1993,  115:  3909 
    Google Scholar
  • 7h Reymond J.-L. Chen Y. J. Org. Chem.  1995,  60:  6970 
    Google Scholar
  • 7i Kumareswaran R. Vankar YD. Synth. Commun.  1998,  28:  2291 
    Google Scholar
  • 7j Larock RC. Yum EK. Yang H. Tetrahedron  1994,  50:  305 
    Google Scholar
  • 7k Basavaiah D. Muthukumaran K. Tetrahedron  1998,  54:  4943 
    Google Scholar
  • 7l Ferreira BRV. Pirovani RV. Souza-Filho LG. Coelho F. Tetrahedron  2009,  65:  7712 
    Google Scholar
  • 7m Sidler DR. Sager JW. Bergan JJ. Wells KM. Bhupathy M. Volante RP. Tetrahedron: Asymmetry  1997,  8:  161 
    Google Scholar
  • 7n Kim JM. Kim KH. Kim TH. Kim JN. Tetrahedron Lett.  2008,  49:  7712 
    Google Scholar
  • 7o Ohno H. Okumura M. Maeda S.-i. Iwasaki H. Wakayama R. Tanaka T. J. Org. Chem.  2003,  68:  7722 
    Google Scholar
  • For domino reactions, see:
  • 8a Dyker G. Thöne A.
    J. Prakt. Chem.  1993,  341:  138 
    Google Scholar
  • 8b Dyker G. Kadzimirsz D. Henkel G. Tetrahedron Lett.  2003,  44:  7905 
    Google Scholar
  • 8c Catellani M. Deledda S. Ganchegui B. Hénin F. Motti E. Muzart J. J. Organomet. Chem.  2003,  687:  473 
    Google Scholar
  • 8d Dyker G. Grundt P. Markwitz H. Henkel G. J. Org. Chem.  1998,  63:  6043 
    Google Scholar
  • 9a Tietze LF. Kahle K. Raschke T. Chem. Eur. J.  2002,  8:  401 
    Google Scholar
  • 9b Bruyére D. Bouyssi D. Balme G. Tetrahedron  2004,  60:  4007 
    Google Scholar
  • 9c Satyanarayana G. Maier ME. Tetrahedron  2008,  64:  356 
    Google Scholar
  • 9d Satyanarayana G. Maier ME. J. Org. Chem.  2008,  73:  5410 
    Google Scholar
  • 9e Gibson (née Thomas) SE. Jones JO. McCague R. Tozer MJ. Whitcombe NJ. Synlett  1999,  954 
    Google Scholar
  • For reports on long-chain allylic alcohols, see:
  • 10a Larock RC. Leung W.-Y. Stolz-Dunn S. Tetrahedron Lett.  1989,  30:  6629 
    Google Scholar
  • 10b Wong Y. Dong X. Larock RC. J. Org. Chem.  2003,  68:  3090 
    Google Scholar
  • 10c Satyanarayana G. Maichle-Mössmer C. Maier ME. Chem. Commun.  2009,  1571 
    Google Scholar
  • 10d Dyker G. Markwitz H. Synthesis  1998,  1750 
    Google Scholar
  • 10e Berthiol F. Doucet H. Santelli M. Synthesis  2005,  3589 
    Google Scholar
  • 10f Cropper EL. Yuen A.-P. Ford A. White AJP. Hii KK. Tetrahedron  2009,  65:  525 
    Google Scholar
  • For intramolecular Heck-type reaction, see:
  • 11a Shi L. Narula CK. Mak KT. Kao L. Xu Y. Heck RF.
    J. Org. Chem.  1983,  48:  3894 
    Google Scholar
  • 11b Gaudin J.-M. Tetrahedron Lett.  1991,  32:  6113 
    Google Scholar
  • 11c Kelly SA. Foricher Y. Mann J. Bentley JM. Org. Biomol. Chem.  2003,  1:  2865 
    Google Scholar
  • 11d Kondo K. Sodeoka M. Mori M. Shibasaki M. Tetrahedron Lett.  1993,  34:  4219 
    Google Scholar
  • 11e Kondo K. Sodeoka M. Mori M. Shibasaki M. Synthesis  1993,  920 
    Google Scholar
  • 11f Dyker G. Grundt P. Eur. J. Org. Chem.  1999,  323 
    Google Scholar
  • 11g Mal SK. Ray D. Ray JK. Tetrahedron Lett.  2004,  45:  277 
    Google Scholar
  • 11h Zawisza AM. Ganchegui B. González I. Bouquillon S. Roglans A. Hénin F. Muzart J. J. Mol. Catal. A: Chem.  2008,  283:  140 
    Google Scholar
  • For β-aryl allylic alcohol synthesis, see:
  • 12a Kang S.-K. Lee H.-W. Jang S.-B. Kim T.-H. Pyun S.-J. J. Org. Chem.  1976,  41:  2604 
    Google Scholar
  • 12b Grasa GA. Singh R. Stevens ED. Nolan SP. J. Organomet. Chem.  2003,  687:  269 
    Google Scholar
  • 12c Kang S.-K. Jung K.-Y. Park C.-H. Namkoong E.-Y. Kim T.-H. Tetrahedron Lett.  1995,  36:  6287 
    Google Scholar
  • 12d

    See ref. 8a.

    Google Scholar
  • 12e Leese MP. Williams JMJ. Synlett  1999,  1645 
    Google Scholar
  • 12f Fang X. Yang X. Yang X. Zhao M. Chen G. Wu F. Tetrahedron Lett.  2006,  47:  8231 
    Google Scholar
  • 12g Alacida E. Nájera C. Adv. Synth. Catal.  2007,  349:  2572 
    Google Scholar
  • 13 Briot A. Baehr C. Brouillard R. Wagner A. Mioskowski C. J. Org. Chem.  2004,  69:  1374 
    Google Scholar