Enolonium Species—Umpoled Enolates
Shlomy Arava
Department of Chemical Sciences, Ariel-University, 40700 Ariel, Israel
Search for more papers by this authorDr. Jayprakash N. Kumar
Department of Chemical Sciences, Ariel-University, 40700 Ariel, Israel
Search for more papers by this authorShimon Maksymenko
Department of Chemical Sciences, Ariel-University, 40700 Ariel, Israel
Search for more papers by this authorDr. Mark A. Iron
Computational Chemistry Unit, Department of Chemical Research Support, Weizmann Institute of Science, 7610001 Rehovot, Israel
Search for more papers by this authorDr. Keshaba N. Parida
Department of Chemical Sciences, Ariel-University, 40700 Ariel, Israel
Search for more papers by this authorDr. Peter Fristrup
Institute of Chemistry, Technical University of Denmark, 2400-Kgs Lyngby, Denmark
Search for more papers by this authorCorresponding Author
Dr. Alex M. Szpilman
Department of Chemical Sciences, Ariel-University, 40700 Ariel, Israel
Search for more papers by this authorShlomy Arava
Department of Chemical Sciences, Ariel-University, 40700 Ariel, Israel
Search for more papers by this authorDr. Jayprakash N. Kumar
Department of Chemical Sciences, Ariel-University, 40700 Ariel, Israel
Search for more papers by this authorShimon Maksymenko
Department of Chemical Sciences, Ariel-University, 40700 Ariel, Israel
Search for more papers by this authorDr. Mark A. Iron
Computational Chemistry Unit, Department of Chemical Research Support, Weizmann Institute of Science, 7610001 Rehovot, Israel
Search for more papers by this authorDr. Keshaba N. Parida
Department of Chemical Sciences, Ariel-University, 40700 Ariel, Israel
Search for more papers by this authorDr. Peter Fristrup
Institute of Chemistry, Technical University of Denmark, 2400-Kgs Lyngby, Denmark
Search for more papers by this authorCorresponding Author
Dr. Alex M. Szpilman
Department of Chemical Sciences, Ariel-University, 40700 Ariel, Israel
Search for more papers by this authorAbstract
Enolonium species/iodo(III)enolates of carbonyl compounds have been suggested to be intermediates in a wide variety of hypervalent iodine induced chemical transformations of ketones, including α-C−O, α-C−N, α-C−C, and α-carbon–halide bond formation, but they have never been characterized. We report that these elusive umpoled enolates may be made as discrete species that are stable for several minutes at −78 °C, and report the first spectroscopic identification of such species. It is shown that enolonium species are direct intermediates in C−O, C−N, C−Cl, and C−C bond forming reactions. Our results open up chemical space for designing a variety of new transformations. We showcase the ability of enolonium species to react with prenyl, crotyl, cinnamyl, and allyl silanes with absolute regioselectivity in up to 92 % yield.
Supporting Information
As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.
| Filename | Description |
|---|---|
| ange201610274-sup-0001-misc_information.pdf3.2 MB | Supplementary |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1
- 1aD. Seebach, Angew. Chem. Int. Ed. Engl. 1979, 18, 239–258; Angew. Chem. 1979, 91, 259–278;
- 1bO. Miyata, T. Miyoshi, M. Ueda, Arkivoc 2013, 60.
- 2
- 2aV. V. Zhdankin, Hypervalent Iodine Chemistry: Preparation, Structure, and Synthetic Applications of Polyvalent Iodine Compounds, Wiley, New York, 2013;
10.1002/9781118341155 Google Scholar
- 2bA. Yoshimura, V. V. Zhdankin, Chem. Rev. 2016, 116, 3328–3435.
- 3E. A. Merritt, B. Olofsson, Synthesis 2011, 517–538.
- 4
- 4aF. Marshall Beringer, P. S. Forgione, M. D. Yudis, Tetrahedron 1960, 8, 49–63;
10.1016/S0040-4020(01)93330-7 Google Scholar
- 4bJ. H. Ryan, P. J. Stang, Tetrahedron Lett. 1997, 38, 5061–5064;
- 4cP. Gao, P. S. Portoghese, J. Org. Chem. 1995, 60, 2276–2278;
- 4dP. Gao, D. L. Larson, P. S. Portoghese, J. Med. Chem. 1998, 41, 3091–3098;
- 4eC. H. Oh, J. S. Kim, H. H. Jung, J. Org. Chem. 1999, 64, 1338–1340;
- 4fZ. Jia, E. Gálvez, R. M. Sebastián, R. Pleixats, Á. Álvarez-Larena, E. Martin, A. Vallribera, A. Shafir, Angew. Chem. Int. Ed. 2014, 53, 11298–11301; Angew. Chem. 2014, 126, 11480–11483.
- 5
- 5aF. M. Beringer, S. A. Galton, J. Org. Chem. 1965, 30, 1930–1934;
- 5bM. D. Bachi, N. Bar-Ner, P. J. Stang, B. L. Williamson, J. Org. Chem. 1993, 58, 7923–7924;
- 5cD. Fernandez Gonzalez, J. P. Brand, J. Waser, Chem. Eur. J. 2010, 16, 9457–9461;
- 5dD. Fernández González, J. P. Brand, R. Mondière, J. Waser, Adv. Synth. Catal. 2013, 355, 1631–1639.
- 6I. Kieltsch, P. Eisenberger, A. Togni, Angew. Chem. Int. Ed. 2007, 46, 754–757; Angew. Chem. 2007, 119, 768–771.
- 7
- 7aO. S. Shneider, E. Pisarevsky, P. Fristrup, A. M. Szpilman, Org. Lett. 2015, 17, 282–285;
- 7bT. A. Targel, J. N. Kumar, O. S. Shneider, S. Bar, N. Fridman, S. Maximenko, A. M. Szpilman, Org. Biomol. Chem. 2015, 13, 2546–2549.
- 8
- 8aF. Mizukami, M. Ando, T. Tanaka, J. Imamura, Bull. Chem. Soc. Jpn. 1978, 51, 335–336;
- 8bM. Ochiai, Y. Takeuchi, T. Katayama, T. Sueda, K. Miyamoto, J. Am. Chem. Soc. 2005, 127, 12244–12245.
- 9G. F. Koser, A. G. Relenyi, A. N. Kalos, L. Rebrovic, R. H. Wettach, J. Org. Chem. 1982, 47, 2487–2489.
- 10P. Mizar, T. Wirth, Angew. Chem. Int. Ed. 2014, 53, 5993–5997; Angew. Chem. 2014, 126, 6103–6107.
- 11
- 11aH. Ibrahim, F. Kleinbeck, A. Togni, Helv. Chim. Acta 2004, 87, 605–610;
- 11bP. B. Thorat, B. Y. Bhong, N. N. Karade, Synlett 2013, 2061–2066.
- 12G. C. Geary, E. G. Hope, K. Singh, A. M. Stuart, RSC Adv. 2015, 5, 16501–16506.
- 13R. Akula, M. Galligan, H. Ibrahim, Chem. Commun. 2009, 6991–6993.
- 14
- 14aS. Sato, M. Yoshida, S. Hara, Synthesis 2005, 2602–2605;
- 14bT. Kitamura, K. Muta, K. Muta, J. Org. Chem. 2014, 79, 5842–5846.
- 15A. S. Ivanov, I. A. Popov, A. I. Boldyrev, V. V. Zhdankin, Angew. Chem. Int. Ed. 2014, 53, 9617–9621; Angew. Chem. 2014, 126, 9771–9775.
- 16R. M. Moriarty, H. Hu, S. C. Gupta, Tetrahedron Lett. 1981, 22, 1283–1286.
- 17P.-O. Norrby, T. B. Petersen, M. Bielawski, B. Olofsson, Chem. Eur. J. 2010, 16, 8251–8254, S8251/8251–S8251/8219.
- 18S. Beaulieu, C. Y. Legault, Chem. Eur. J. 2015, 21, 11206–11211.
- 19
- 19aV. V. Zhdankin, R. Tykwinski, R. Caple, B. Berglund, A. S. Koz'min, N. S. Zefirov, Tetrahedron Lett. 1988, 29, 3703–3704;
- 19bV. V. Zhdankin, M. Mullikin, R. Tykwinski, B. Berglund, R. Caple, N. S. Zefirov, A. S. Koz'min, J. Org. Chem. 1989, 54, 2605–2608.
- 20K. C. Nicolaou, Y. L. Zhong, P. S. Baran, J. Am. Chem. Soc. 2000, 122, 7596–7597.
- 21T. Cuvigny, M. Julia, J. Organomet. Chem. 1987, 331, 121–137.
- 22
- 22aM. J. Koh, R. K. M. Khan, S. Torker, A. H. Hoveyda, Angew. Chem. Int. Ed. 2014, 53, 1968–1972; Angew. Chem. 2014, 126, 1999–2003;
- 22bG. Buchi, D. E. Vogel, J. Org. Chem. 1985, 50, 4664–4665;
- 22cC. Li, B. Breit, J. Am. Chem. Soc. 2014, 136, 862–865.
Citing Literature
This is the
German version
of Angewandte Chemie.
Note for articles published since 1962:
Do not cite this version alone.
Take me to the International Edition version with citable page numbers, DOI, and citation export.
We apologize for the inconvenience.
