Authors:
Toshiya Yoshiiwa Kyushu University Interdisciplinary Graduate School of Engineering Sciences 6–1 Kasuga-koen Kasuga 816-8580 Japan

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Satoshi Umezu Kyushu University Interdisciplinary Graduate School of Engineering Sciences 6–1 Kasuga-koen Kasuga 816-8580 Japan

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Manabu Tokeshi Hokkaido University Faculty of Engineering Kita 13 Nishi 8, Kita-ku Sapporo 060-8628 Japan

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Yoshinobu Baba Nagoya University, Furo-cho Graduate School of Engineering Chikusa-ku Nagoya 464-8603 Japan

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Mitsuru Shindo Kyushu University Institute for Materials Chemistry and Engineering 6–1 Kasuga-koen Kasuga 816-8580 Japan

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We report a method for the generation and subsequent reaction of ynolates in a flow microreactor via a stop-flow process. This procedure allowed for the synthesis of ynolates at ambient temperature within 11 min via a Li–Br exchange reaction with sec-butyllithium, whereas the corresponding batch process generally requires low temperature control and extended reaction times of up to 1 h. The stop-flow method is especially useful for optimizing the reaction time without having to use various microtube lengths. The resulting ynolates were applied to the olefination of carbonyl compounds and to pyrrole synthesis. These results indicate the practical utility of the ynolate reaction and should contribute to progress in flash chemistry.

  • For reviews, see: (a) Shindo, M. Tetrahedron2007, 63, 10–36; (b) Shindo, M. The Chemistry of Metal Ynolates. In The Chemistry of Metal Enolates; Patai Series: The Chemistry of Functional Groups; Zabicky, J., Ed.; John Wiley & Sons, Chichester, UK, 2009; 739–786.

  • (a) Shindo, M.; Sato, Y.; Shishido, K. Tetrahedron1998, 54, 2411–2422; (b) Shindo, M.; Matsumoto, K.; Shishido, K. Org. Synth. 2007, 84, 11–21.

  • Umezu, S.; Yoshiiwa, T.; Tokeshi, M.; Shindo, M. Tetrahedron Lett.2014, 55, 1822–1825.

  • (a) Shindo, M.; Sato, Y.; Shishido, K.; J. Org. Chem.2000, 65, 5443–5445; (b) Shindo, M.; Matsumoto, K.; Mori, S.; Shishido, K. J. Am. Chem. Soc. 2002, 124, 6840–6841; (c) Shindo, M.; Sato, Y.; Yoshikawa, T.; Koretsune, R.; Shishido, K. J. Org. Chem. 2004, 69, 3912–3916; (d) Mori, S.; Shindo, M. Org. Lett.2004, 6, 3945–3948; (e) Shindo, M.; Yoshikawa, T.; Itou, Y.; Mori, S.; Nishii, T.; Shishido, K. Chem. Eur. J. 2006, 12, 524–536; (f) Shindo, M.; Kita, T.; Kumagai, T.; Matsumoto, K.; Shishido, K. J. Am. Chem. Soc. 2006, 128, 1062–1063; (g) Yoshikawa, T.; Mori, S.; Shindo, M. J. Am. Chem. Soc.2009, 131, 2092–2093; (h) Umezu, S.; Shindo, M. Tetrahedron Lett. 2013, 54, 6871–6873. For reviews, see: (i) Shindo, M.; Mori, S. Synlett2008, 2231–2243; (j) Shindo, M.; Matsumoto, K. Top. Curr. Chem. 2012, 327, 1–32.

  • (a) Shindo, M.; Sato, Y.; Shishido, K. J. Am. Chem. Soc.1999, 121, 6507–6508; (b) Shindo, M.; Matsumoto, K.; Sato, Y.; Shishido, K. Org. Lett. 2001, 3, 2029–2031; (c) Shindo, M.; Sato, Y.; Shishido, K. J. Org. Chem. 2001, 66, 7818–7824.

  • Shindo, M.; Yoshimura, Y.; Hayashi, M.; Soejima, H.; Yoshikawa, T.; Matsumoto, K.; Shishido, K. Org Lett.2007, 9, 1963–1966.

  • (a) Haner, R., Laube, T., Seebach, D. J. Am. Chem. Soc.1985, 107, 5396–5403; (b) Tomioka, K., Shindo, M., Koga, K. J. Org. Chem.1990, 55, 2276–2277.

  • Bates, R. B.; Kroposki, L. M.; Potter, D. E. J. Org. Chem.1972, 37, 560–562.

  • (a) Suga, S.; Yamada, D.; Yoshida, J. Chem Lett.2010, 39, 404–406. For recent reviews, see: (b) Ley, S. V. Chem. Rec. 2012, 12, 378–390; (c) Wegner, J.; Ceylan, S.; Kirschning, A. Adv. Synth. Catal. 2012, 354, 17–57; (d) Wegner, J.; Ceylan, S.; Kirschning, A. Chem. Commun. 2011, 47, 4583–4592; (e) Geyer, K.; Gustafsson, T.; Seeberger, P. H. Synlett2009, 2382–2391; (f) Yoshida, J.; Nagaki, A.; Yamada, T. Chem. Eur. J. 2008, 14, 7450–7459; (g) Fukuyama, T.; Rahman, M. T.; Sato, M.; Ryu, I. Synlett2008, 151–163.

  • Representative lithium/halogen exchange reactions in flow microreactors: (a) Usutani, H.; Tomida, Y.; Nagaki, A.; Okamoto, H.; Nokami, T.; Yoshida, J. J. Am. Chem. Soc. 2007, 129, 3046–3047; (b) Nagaki, A.; Tomida, Y.; Usutani, H.; Kim. H.; Takabayashi, N.; Nokami, T.; Okamoto, H.; Yoshida, J. Chem. Asian J.2007, 2, 1513–1523; (c) Nagaki, A.; Kim, H.; Yoshida, J. Angew. Chem., Int. Ed.2008, 47, 7833–7836; (d) Goto, S.; Velder, J.; Sheikh, S. E.; Sakamoto, Y.; Mitani, M.; Elmas, S.; Adler, A.; Becker, A.; Neudorfl, J.-M.; Lex, J.; Schmalz, H.-G. Synlett2008, 1361–1365; (e) Tomida, Y.; Nagaki, A.; Yoshida, J. Org. Lett.2009, 11, 3614–3617; (f) Nagaki, A.; Kim, H.; Yoshida, J. Angew. Chem., Int. Ed. 2009, 48, 8063–8065; (g) Nagaki, A.; Takizawa, E.; Yoshida, J. J. Am. Chem. Soc.2009, 131, 1654–1655; (h) Nagaki, A.; Kenmoku, A.; Moriwaki, Y.; Hayashi, A.; Yoshida, J. Angew. Chem., Int. Ed.2010, 49, 7543–7547; (i) Nagaki, A.; Kim, H.; Usutani, H.; Matsuo, C.; Yoshida, J. Org. Biomol. Chem.2010, 8, 1212–1217; (j) Asai, T.; Takata, A.; Ushiogi, Y.; Iinuma, Y.; Nagaki, A.; Yoshida, J. Chem. Lett.2011, 40, 393–395; (k) Nagaki, A,; Yamada, S.; Doi, M.; Tomida, Y.; Takabayashi, N.; Yoshida, J. Green Chem.2011, 13, 1110–1113; (l) Kim. H.; Nagaki, A.; Yoshida, J. Nature Commun.2011, 2, 1264/1–1264/2; (m) Nagaki, A.; Takahashi, Y.; Yamada, S.; Matsuo, C.; Haraki, S.; Moriwaki, Y.; Kim, S.; Yoshida, J. J. Flow. Chem.2012, 2, 70–72; (n) Nagaki, A.; Matsuo, C.; Kim, S.; Saito, K.; Miyazaki, A.; Yoshida, J. Angew. Chem., Int. Ed.2012, 51, 3245–3248; (o) Nagaki, A.; Ichinari, D.; Yoshida, J. Chem. Commun. 2013, 49, 3242–3244; (p) Nagaki, A.; Uesugi, Y.; Kim, H.; Yoshida, J. Chem. Asian J. 2013, 8, 705–708; (q) Nagaki, A. J. Synth. Org. Chem., Jpn.2013, 71, 1002–1019.

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Journal of Flow Chemistry
Language English
Size A4
Year of
Foundation
2011
Volumes
per Year
1
Issues
per Year
4
Founder Áramlásos Kémiai Tudományos Társaság
Founder's
Address
H-1031 Budapest, Hungary Záhony utca 7.
Publisher Akadémiai Kiadó
Springer Nature Switzerland AG
Publisher's
Address
H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
CH-6330 Cham, Switzerland Gewerbestrasse 11
Responsible
Publisher
Chief Executive Officer, Akadémiai Kiadó
ISSN 2062-249X (Print)
ISSN 2063-0212 (Online)