Synthesis 2006(9): 1518-1536  
DOI: 10.1055/s-2006-926428
PAPER
© Georg Thieme Verlag Stuttgart · New York

Heck Reaction of Protected Alk-1-en-3-ol, -4-ols, -5-ol or -6-ol with Aryl Bromides Catalysed by a Palladium Complex Derived from a Tetraphosphine

Florian Berthiol, Henri Doucet*, Maurice Santelli*
UMR 6180 CNRS and Université d’Aix-Marseille III: ‘Chirotechnologies: catalyse et biocatalyse’, Laboratoire de Synthèse Organique, Faculté des Sciences de Saint Jérôme, Université d’Aix-Marseille III, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France
Fax: +33(491)983865; e-Mail: henri.doucet@univ.u-3mrs.fr; e-Mail: m.santelli@univ.u-3mrs.fr;
Further Information

Publication History

Received 7 November 2005
Publication Date:
11 April 2006 (eFirst)

Abstract

The tetraphosphine cis,cis,cis-1,2,3,4-tetrakis(diphenyl­phosphinomethyl)cyclopentane in combination with [Pd(C3H5)Cl]2 affords a very efficient catalyst for the Heck reaction of protected alk-1-en-3-ols, -4-ols, -5-ols or -6-ols with aryl bromides. With 3-benzyloxyhex-1-ene or 4-benzyloxypent-1-ene, the (E)-1-aryl-3-benzyloxyhex-1-ene or (E)-1-aryl-4-benzyloxypent-1-ene derivatives were regio- and stereoselectively obtained. The protected ethylenic­ primary alcohols 4-benzyloxybut-1-ene, 4-tetrahydropyranyloxybut-1-ene, 5-tetrahydropyranyloxypent-1-ene and 6-tetrahydropyranyloxyhex-1-ene led in general to the (E)-1-aryl-4-benzyloxybut-1-ene or (E)-1-aryltetrahydropyranyloxyalk-1-enes as major isomers. However, with these substrates, the migration of the double bond was observed, and mixtures of isomers were obtained in most cases. The selectivities of the reactions depend both on electronic and steric factors. With electron-poor aryl bromides higher selectivities in favour of 1-arylalk-1-enol derivatives were generally obtained than with electron-rich aryl bromides. In the presence of sterically congested aryl bromides, larger amounts of products resulting from the migration of the double bond were observed. For example from 2,4,6-triisopropylbromobenzene and 6-tetrahydropyranyloxyhex-1-ene, 6-(2,4,6-triisopropylphenyl)hexanal was obtained as major product after deprotection. For most of these reactions, similar reactions-rates were observed with electron-poor and electron-rich aryl bromides. Several reactions can be performed with as little as 0.1% catalyst.

    References

  • 1 de Meijere A. Meyer F. Angew. Chem., Int. Ed. Engl.  1994,  33:  2379 
  • 2 Reetz MT. In Transition Metal Catalysed Reactions   Davies SG. Murahashi S.-I. Blackwell; Oxford: 1999. 
  • 3 Beletskaya I. Cheprakov A. Chem. Rev.  2000,  100:  3009 
  • 4 Whitcombe N. Hii KKM. Gibson S. Tetrahedron  2001,  57:  7449 
  • 5 Littke A. Fu G. Angew. Chem. Int. Ed.  2002,  41:  4176 
  • 6 Farina V. Adv. Synth. Catal.  2004,  346:  1553 
  • 7 Jeffery T. Chem. Commun.  2005,  1287 
  • 8 Muzart J. Tetrahedron  2005,  61:  4179 
  • 9 Ono K. Fugami K. Tanaka S. Tamaru Y. Tetrahedron Lett.  1994,  35:  4133 
  • 10 Fukuyama T. Chen X. Peng G. J. Am. Chem. Soc.  1994,  116:  3127 
  • 11 Motoba K. Motofusa S.-I. Cho CS. Ohe K. Uemura S. J. Organomet. Chem.  1999,  574: 
  • 12 Nokami J. Furukawa A. Okuda Y. Hazato A. Kurozumi S. Tetrahedron Lett.  1998,  39:  1005 
  • 13 Tripathy NK. Georg GI. Tetrahedron Lett.  2004,  45:  5309 
  • 14 Berthiol F. Doucet H. Santelli M. Eur. J. Org. Chem.  2005,  1367 
  • 15 Laurenti D. Feuerstein M. Pèpe G. Doucet H. Santelli M. J. Org. Chem.  2001,  66:  1633 
  • 16 Feuerstein M. Laurenti D. Bougeant C. Doucet H. Santelli M. Chem. Commun.  2001,  325 
  • 17 Feuerstein M. Berthiol F. Doucet H. Santelli M. Org. Biomol. Chem.  2003,  1:  2235 
  • 18 Feuerstein M. Doucet H. Santelli M. J. Org. Chem.  2001,  66:  5923 
  • 19 Feuerstein M. Doucet H. Santelli M. Synlett  2001,  1980 
  • 20 Feuerstein M. Doucet H. Santelli M. Tetrahedron Lett.  2002,  43:  2191 
  • 21 Berthiol F. Feuerstein M. Doucet H. Santelli M. Tetrahedron Lett.  2002,  43:  5625 
  • 22 Berthiol F. Doucet H. Santelli M. Tetrahedron Lett.  2003,  44:  1221 
  • 23 Berthiol F. Doucet H. Santelli M. Synlett  2003,  841 
  • 24 Kondolff I. Doucet H. Santelli M. Tetrahedron Lett.  2003,  44:  8487 
  • 25 Kondolff I. Doucet H. Santelli M. Synlett  2004,  1561 
  • 26 Berthiol F. Doucet H. Santelli M. Tetrahedron Lett.  2004,  45:  5633 
  • 27 Lemhadri M. Doucet H. Santelli M. Tetrahedron  2004,  50:  11533 
  • 28 Berthiol F. Doucet H. Santelli M. Synthesis  2005,  3589