Palladium-catalyzed γ -selective and stereospecific allyl-aryl coupling between allylic acetates and arylboronic acids

Journal of the American Chemical Society

Volumn 130, Issue 51, 2008, Pages 17276-17277

  Ohmiya, Hirohisa ^a   Makida, Yusuke ^a   Tanaka, Tatsunori ^a   Sawamura, Masaya ^a  

^a HOKKAIDO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ARYLBORONIC ACIDS; BENZYLIC; CATALYTIC AMOUNTS; CHIRALITY TRANSFER; COUPLING PRODUCT; OPTICALLY ACTIVE; PHENANTHROLINE; STEREOGENIC CENTERS; STEREOSPECIFIC;

ACIDS; PALLADIUM; STEREOCHEMISTRY; SULFUR COMPOUNDS;

ORGANOMETALLICS;

ACETIC ACID DERIVATIVE; ALLYL COMPOUND; BORONIC ACID DERIVATIVE; PALLADIUM; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL REACTION; ENANTIOSELECTIVITY; STEREOSPECIFICITY;

EID: 67749108290     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja808673n     Document Type: Article

References (24)

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4. Even for Cu-catalyzed systems, studies to date have focused largely on the reactions of primary allylic electrophiles that give terminal alkenes. For a review on enantioselective allyic substitutions catalyzed by chiral copper complexes, see: Yorimitsu, H. ; Oshima, K. Angew. Chem., Int. Ed. 2005, 44, 4435-4439.
5. For γ -selective allylic substitution reactions with stoichiometric arylcopper(I) reagents with excellent 1, 3-chirality transfer, see: (a) Harrington-Frost, N. ; Leuser, H. ; Calaza, M. I. ; Kneisel, F. F. ; Knochel, P. Org. Lett. 2003, 5, 2111-2114.
6. (b) Kiyotsuka, Y. ; Acharya, H. P. ; Katayama, Y. ; Hyodo, T. ; Kobayashi, Y. Org. Lett. 2008, 10, 1719-1722.
7. For related studies from our group (Cu-catalyzed regioselective allylic and propargylic substitutions with diboron), see: (a) Ito, H. ; Kawakami, C. ; Sawamura, M. J. Am. Chem. Soc. 2005, 127, 16034-16035.
8. (b) Ito, H. ; Ito, S. ; Sasaki, Y. ; Matsuura, K. ; Sawamura, M. J. Am. Chem. Soc. 2007, 129, 14856-14857.
9. (c) Ito, H. ; Kosaka, Y. ; Nonoyama, K. ; Sasaki, Y. ; Sawamura, M. Angew. Chem., Int. Ed. 2008, 47, 7424-7427.
10. (d) Ito, H. ; Sasaki, Y. ; Sawamura, M. J. Am. Chem. Soc. 2008, 130, 15774-15775.
11. Pd-catalyzed γ -selective allyl-aryl coupling between aryl iodides and allylic acetates has been reported. However, the reaction required harsh conditions (typically 180 ° C) and is not stereoselective. See: Mariamphillai, B. ; Herse, C. ; Lautens, M. Org. Lett. 2005, 7, 4745-4747.
12. Maddaford reported the Pd-catalyzed C-glycosidation of peracetylated glycals (γ -substitution of γ -alkoxy-substituted allylic acetates with anti-stereochemistry) with arylboronic acids. This reaction goes through a (π -allyl)palladium(II) intermediate. The regioselectivity is controlled by the electronic effect of the oxygen functionality and is limited to this specific substrate class. See: Ramanauth, J. ; Poulin, O. ; Rakhit, S. ; Maddaford, S. P. Org. Lett. 2001, 3, 2013-2015.
13. 2-carbon coupling between allyl alcohol derivatives and organoboron compound via a (π -allyl)palladium(II) intermediate, see: (a) Miyaura, N. ; Yamada, K. ; Suginome, H. ; Suzuki, A. J. Am. Chem. Soc. 1985, 107, 972-980.
14. (b) Legros, J. -Y. ; Fiaud, J. -C. Tetrahedron Lett. 1990, 31, 7453-7456.
15. (c) Uozumi, Y. ; Danjo, H. ; Hayashi, T. J. Org. Chem. 1999, 64, 3384-3388, See also ref 6.
16. For Pd-catalyzed oxidative Mizoroki-Heck-type reactions of allylic acetates with arylboronic acids, see: (a) Delcamp, J. H. ; White, M. C. J. Am. Chem. Soc. 2006, 128, 15076-15077.
17. (b) Ruan, J. ; Li, X. ; Saidi, O. ; Xiao, J. J. Am. Chem. Soc. 2008, 130, 2424-2425.
18. This result is in sharp contrast to the fact that the regioselectivity in the transition metal catalyzed allylic substitutions that involve a (π -allyl)metal intermediate is highly dependent on the substitution pattern of allylic substrates. For reviews on Pd-catalyzed allylic substitution reactions, see ref 1c. See also ref 7.
19. For Schemes 1 and 2 and Table 1, the crude materials after removal of the catalyst and boron compounds consisted of the coupling product (2), biaryl, unreacted allylic acetate (1), and/or unidentified compounds. The Mizoroki-Heck-type product was not detected. The isolated products were contaminated with traces of unidentified materials (0. 1-5%). The isolated yields for the reaction of 1f, g, h, i in Table 1 and Scheme 2 may be reduced by the evaporation of the products.
20. The reaction of terminal alkenes 1d and 1h were carried out with THF solvent (Table 1, entries 9 and 13). The use of THF suppressed the formation of unidentified side products.
21. 2, see: Moreno-Mañ as, M. ; Perez, M. ; Pleixats, R. J. Org. Chem. 1996, 61, 2346-2351.
22. (a) Alkene products derived by β -hydride elimination from alkylpalladium intermediate D were not observed (see ref 10). This is contradictory with the reported results of the oxidative Mizoroki-Heck-type arylation of allylic esters with arylboronic acid. See ref 8. For Mizoroki-Heck-type arylation of allylic acetates with aryl iodides, see:
23. (b) Pan, D. ; Chen, A. ; Su, Y. ; Zhou, W. ; Li, S. ; Jia, W. ; Xiao, J. ; Liu, Q. ; Zhang, L. ; Jiao, N. Angew. Chem., Int. Ed. 2008, 47, 4729-4732.
24. Since π -complex C (C′ ) is a normal 16-electron square planar complex, the acetoxy group of C (C′ ) should be uncoordinated. Although both diastereomeric π -complexes may form, the description of equilibrium with the nonproductive diastereomer is omitted in Scheme 4.