Jump to ContentJump to Main Navigation
Show Summary Details
More options …

Pure and Applied Chemistry

The Scientific Journal of IUPAC

Ed. by Burrows, Hugh / Stohner, Jürgen


IMPACT FACTOR 2017: 5.294

CiteScore 2017: 3.42

SCImago Journal Rank (SJR) 2017: 1.212
Source Normalized Impact per Paper (SNIP) 2017: 1.546

Online
ISSN
1365-3075
See all formats and pricing
More options …
Volume 86, Issue 3

Issues

Transition-metal clusters as catalysts for chemoselective transesterification of alcohols in the presence of amines

Kazushi Mashima
  • Corresponding author
  • Department of Chemistry, Graduate School of Engineering Science, Osaka University and CREST, JST, Toyonaka, Osaka 560-8531, Japan
  • Email
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Yukiko Hayashi
  • Department of Chemistry, Graduate School of Engineering Science, Osaka University and CREST, JST, Toyonaka, Osaka 560-8531, Japan
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Kazushi Agura
  • Graduate School of Pharmaceutical Sciences, Kyusyu University and CREST, JST, Fukuoka 812-8582, Japan
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Takashi Ohshima
  • Corresponding author
  • Graduate School of Pharmaceutical Sciences, Kyusyu University and CREST, JST, Fukuoka 812-8582, Japan
  • Email
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
Published Online: 2014-03-04 | DOI: https://doi.org/10.1515/pac-2014-5036

Abstract

Acylation is one of the most abundant organic transformations of alcohols (esterification) and amines (amidation). Because of the greater nucleophilicity of the amino group compared to the hydroxyl group and the stability of amides compared to esters, N-acylation occurs predominantly in organic synthetic reactions. We reported that the μ-oxo-tetranuclear zinc cluster Zn4(OCOCF3)6O efficiently catalyzes highly chemoselective acylation of hydroxyl groups in the presence of primary and secondary alkyl amino groups to afford the corresponding esters in high yields. Not only zinc carboxylate complexes but also various carboxylate complexes of first-row late transition metals, such as Mn, Fe, Co, and Cu, become catalysts for such the hydroxy group-selective acylation in the presence of amines. Among these carboxylate compounds, we found that the combination of an octanuclear cobalt carboxylate cluster [Co4(OCOR)6O]2 (R = CF3, CH3, and tBu) with nitrogen-containing ligands such as 2,2′-bipyridine show sufficient catalytic activity toward O-selective transesterification. Notably, an alkoxide-bridged dinuclear complex, Co2(OCOtBu)2(bpy)22-OCH2-C6H4-4-CH3)2, was successfully isolated as a key intermediate that proceeds with Michaelis–Menten behavior through an ordered ternary complex mechanism similar to dinuclear metallo-enzymes, suggesting that the formation of alkoxides, followed by coordination of the ester, is responsible for the unique O-selective acylation.

Keywords: acylation; catalysts; chemoselectivity; clusters; cobalt; OMCOS-17; zinc

References

  • [1]

    For reviews, see: (a) J. Mulzer, in Comprehensive Organic Synthesis B. M. Trost, I. Fleming (Eds.), Vol. 6, Pergamon Press, New York (1992); (b) J. Otera. In Esterification, Wiley-VCH, Weinheim (2003); (c) J. Otera. Chem. Rev. 93, 1449 (1993); (d) R. C. Larock. In Comprehensive Organic Transformations, 2nd ed., Wiley-VCH, New York (1999); (e) M. B. Smith. In Compendium of Organic Synthetic Methods, Vol. 9, p. 100, John Wiley, New York (2001); (f) H. E. Hoydonckx, D. E. De Vos, S. A. Chavan, P. A. Jacobs. Top. Catal. 27, 83 (2004); (g) G. A. Grasa, R. Singh, S. P. Nolan. Synthesis 971 (2004); (h) C. A. G. N. Montalbetti, V. Falque, M. Park. Tetrahedron 61, 10827 (2005).Google Scholar

  • [2]

    For reviews, see: (a) M. Nahmany, A. Melman. Org. Biomol. Chem. 2, 1563 (2004); (b) N. A. Afagh, A. K. Yudin. Angew. Chem., Int. Ed. 49, 262 (2010); (c) T. E. Kristensen, T. Hansen. Eur. J. Org. Chem. 3179 (2010); (d) J. Mahatthananchai, A. M. Dumas, J. W. Bode. Angew. Chem., Int. Ed. 51, 10954 (2012); (e) D. J. Trader, E. E. Carlson. Mol. BioSyst. 8, 2484 (2012).Google Scholar

  • [3]

    Y. Tachibana, H. Kawasaki, N. Kihara, T. Takata. J. Org. Chem. 71, 5093 (2006).Google Scholar

  • [4]

    H. Morawetz, E. J. Sammak. J. Phys. Chem. 61, 1357 (1957).Google Scholar

  • [5]

    S. Nagaoka, A. Shundo, T. Satoh, K. Nagira, R. Kishi, K. Ueno, K. Iio, H. Ihara. Synth. Commun. 35, 2529 (2005).Google Scholar

  • [6]

    B. R. Brown, J. Cocker. J. Chem. Res., Synop. 2, 46 (1984).Google Scholar

  • [7]

    T. Mukaiama, F.-C. Pai, M. Onaka, K. Narasaka. Chem. Lett. 9, 563 (1980).CrossrefGoogle Scholar

  • [8]

    S. D. Sarkar, S. Grimme, A. Studer. J. Am. Chem. Soc. 132, 1190 (2010).Google Scholar

  • [9]

    J. H. Maeng, R. L. Funk. Org. Lett. 4, 331 (2002).Google Scholar

  • [10]

    M. Marchini, M. Mingozzi, R. Colombo, C. Gennari, M. Durini, U. Piarulli. Tetrahedron 66, 9528 (2010).CrossrefGoogle Scholar

  • [11]

    L. Gardossi, D. Bianchi, A. M. Klibanov. J. Am. Chem. Soc. 113, 6328 (1991).Google Scholar

  • [12]

    M. Cammenberg, K. Hult, S. Park. Chem. Bio. Chem. 7, 1745 (2006).Google Scholar

  • [13]

    M.-H. Lin, T. V. RajanBabu. Org. Lett. 2, 997 (2000).Google Scholar

  • [14]

    (a) M. Hatano, Y. Furuya, T. Shimmura, K. Moriyama, S. Kamiya, T. Maki, K. Ishihara. Org. Lett. 13, 426 (2011); (b) M. Hatano, S. Kamiya, K. Moriyama, K. Ishihara. Org. Lett. 13, 430 (2011); (c) M. Hatano, S. Kamiya, K. Ishihara. Chem. Commun. 48, 9465 (2012).Google Scholar

  • [15]

    (a) T. Ohshima, T. Iwasaki, K. Mashima. Chem. Commun. 2711 (2006); (b) T. Ohshima, T. Iwasaki, Y. Maegawa, A. Yoshiyama, K. Mashima. J. Am. Chem. Soc. 130, 2944 (2008); (c) T. Iwasaki, Y. Maegawa, Y. Hayashi, T. Ohshima, K. Mashima. J. Org. Chem. 73, 5147 (2008); (d) T. Iwasaki, Y. Maegawa, Y. Hayashi, T. Ohshima, K. Mashima. Synlett 1659 (2009); (e) T. Iwasaki, K. Agura, Y. Maegawa, Y. Hayashi, T. Ohshima, K. Mashima. Chem.—Eur. J. 16, 11567 (2010); (f) Y. Hayashi, T. Ohshima, Y. Fujii, Y. Matsushima, K. Mashima. Catal. Sci. Technol. 1, 230 (2011); (g) Y. Maegawa, K. Agura, Y. Hayashi, T. Ohshima, K. Mashima. Synlett 23, 137 (2012); (h) Y. Maegawa, T. Ohshima, Y. Hayashi, K. Agura, T. Iwasaki, K. Mashima. ACS Catal. 1, 1178 (2011); (i) Y. Hayashi, S. Santoro, Y. Azuma, F. Himo, T. Ohshima, K. Mashima. J. Am. Chem. Soc. 135, 6192 (2013).Google Scholar

  • [16]

    A. A. Sidorov, I. G. Fomina, M. O. Ponina, G. G. Aleksandrov, S. E. Nefedov, I. L. Eremenko, I. I. Moiseev. Russ. Chem. Bull., Int. Ed. 49, 958 (2000).Google Scholar

About the article

Corresponding authors: Kazushi Mashima, Department of Chemistry, Graduate School of Engineering Science, Osaka University and CREST, JST, Toyonaka, Osaka 560-8531, Japan, e-mail: mashima@chem.es.osaka-u.ac.jp and Takashi Ohshima, Graduate School of Pharmaceutical Sciences, Kyusyu University and CREST, JST, Fukuoka 812-8582, Japan, e-mail: ohshima@phar.kyushu-u.ac.jp


Published Online: 2014-03-04

Published in Print: 2014-03-20


Citation Information: Pure and Applied Chemistry, Volume 86, Issue 3, Pages 335–343, ISSN (Online) 1365-3075, ISSN (Print) 0033-4545, DOI: https://doi.org/10.1515/pac-2014-5036.

Export Citation

©2014 by IUPAC & De Gruyter.Get Permission

Citing Articles

Here you can find all Crossref-listed publications in which this article is cited. If you would like to receive automatic email messages as soon as this article is cited in other publications, simply activate the “Citation Alert” on the top of this page.

[1]
Shinji Tanaka, Takuya Nakashima, Toshie Maeda, Manussada Ratanasak, Jun-ya Hasegawa, Yoshihiro Kon, Masanori Tamura, and Kazuhiko Sato
ACS Catalysis, 2018, Page 1097
[2]
Ming-Uei Hung, Shu-Ting Yang, Mani Ramanathan, and Shiuh-Tzung Liu
Applied Organometallic Chemistry, 2017, Page e3976
[3]
Da-Wei Huang, Yi-Hung Liu, Shie-Ming Peng, and Shiuh-Tzung Liu
Dalton Trans., 2016, Volume 45, Number 19, Page 8265
[4]
Da-wei Huang, Yi-Hung Liu, Shie-Ming Peng, and Shiuh-Tzung Liu
Organometallics, 2016, Volume 35, Number 2, Page 151
[5]
Guoqi Zhang, Yi-Xia Jia, Wenbo Chen, Wen-Feng Lo, Nyeisha Brathwaite, James A. Golen, and Arnold L. Rheingold
RSC Adv., 2015, Volume 5, Number 21, Page 15870
[6]
Kazushi Mashima, Yukiko Hayashi, Kazushi Agura, and Takashi Ohshima
ChemInform, 2014, Volume 45, Number 45, Page no

Comments (0)

Please log in or register to comment.
Log in